Conducting polymers at low temperatures and high magnetic fields

Advances in the synthesis of organic conducting polymer systems has increased the electrical conductivity of these systems by several orders of magnitude in the last decade. Several practical applications are envisioned for such systems, but a thorough understanding of the conduction mechanisms and identification of the charge carriers is lacking, making design and implementation for bulk synthesis difficult. In order to clarify our understanding of the electrical properties of these systems, the resistivity and magnetoresistivity of various polymers doped near the metal - insulator transition, such as polyaniline protonated by camphor sulfonic acid (PANi-CSA) and polypyrrole doped with PF₆ (PPy-PF₆), have been studied down to 25 mK in magnetic fields up to 16 T.     

Electrical and Optical Properties of Conducting Polymer - Fullerene and Conducting Polymer - Carbon Nanotube Composites

Various novel photo-physical properties such as a drastic photoluminescence quenching and photoconductivity enhancement and a photo-induced enhancement of low-field microwave absorption due to a highly effective photo-induced electron transfer have been observed in various conducting polymers doped with fullerenes and also acceptor-type molecules and conducting polymers. New types of junction devices utilizing effective charge separation at the interface of conducting polymer/C₆₀, C₆₀-doped conducting polymer/C₆₀ and acceptor type conducting polymer / donor type conducting polymer have been proposed and their novel characteristics have been demonstrated. Novel concepts such as an interpenetrating network, a condensed interface and the effect of introduction of photo-harvesting antenna molecule at the interface have been discussed. Nano-composite films of carbon nanotube (NT) and conducting polymer were prepared. With increasing the volume fraction of NT in conducting polymer the conductivity increases drastically at relatively low concentration of NT, which can be explained in terms of conduction by percolation process. Enhancement of photoconductivity of composite films has been found at near percolation threshold. Heterojunctions made of carbon NT and conducting polymer have also been found to be photosensitive.     

Electrical transport and EPR investigations: A comparative study for d.c. conduction mechanism in monovalent and multivalent ions doped polyaniline

A detailed comparative study of electron paramagnetic resonance (EPR) in conjunction with d.c. electrical conductivity has been undertaken to know about the charge transport mechanism in polyaniline (PANI) doped with monovalent and multivalent protonic acids. This work is in continuation of our previous work for further understanding the conduction mechanism in conducting polymers. The results reveal that the polarons and bipolarons are the main charge carriers formed during doping process and these cause increase in electrical conductivity not only by increase in their concentration but also because of their enhanced mobility due to increased inter-chain transport in polyaniline at high doping levels. EPR line asymmetry having Dysonian line shape for highly doped samples shows a marked deviation of amplitudes A/B ratio from values close to one to much high values as usually observed in metals, thereby support the idea of high conductivity at higher doping levels. The nature of dopant ions and their doping levels control the charge carriers concentration as well as electrical conductivity of polyaniline. The electrical conductivity has also been studied as a function of temperature to know the thermally assisted transport process of these charge carriers at different doping levels which has been found to follow the Mott??s variable range hopping (VRH) conduction model for all the three dopants used. The charge carriers show a change over from 3D VRH to quasi 1D VRH hopping process for multivalent ions at higher doping levels whereas 1D VRH has been followed by monovalent ion for full doping range. These studies collectively give evidence of inter-chain percolation at higher doping levels causing increase in effective mobility of the charge carriers which mainly seems to govern the electrical conduction behaviour in this system.     

An experimental investigation of electrical conductivities in biopolymers

Gum arabica obtained from acacia plant is a conducting biopolymer. Experiments are carried out on this natural gum arabica. In the present study TGA, ion transference number, transient ionic current, thermal analysis, frequency and temperature variation of a.c. conductivity, Arrhenius plot and volt-ampere characteristics of specimens are carried out. The total electrical conductivity of these biopolymers are comparable to that of synthetic polymers doped with inorganic salts. The ion transference number of these biopolymers show their superionic nature of electrical conduction. The overall conduction mechanism seems to be protonic in nature rather than electronic one.     

Anisotropic electrical conduction in gum arabica—a biopolymer

Gum arabica, a natural biopolymer, exhibits electrical properties like conducting polymers. Earlier investigations show its ion-conducting superionic nature rather than its proton conducting nature with room temperature d.c. conductivity 10e−07 S/cm. The present study shows more interesting electrical characters gum arabica, XRD study of its powdered sample shows an amorphous nature and that of caste and textured specimen show an increased RDF. The same indicates a possibility of crystallization, which is a difficult task for this solid gel-like substance. Specimen with preferred molecular orientation is prepared by casting thin layer of gum arabica on scratched (10 μm) metal electrode and glass substrate. The desired anisotropy thus produced is confirmed by XRD study. The morphology of ordinarily caste specimen and textured specimen were studied and compared by SEM study. The impedance spectroscopy carried over this specimen shows an electrical conductivity like that of crystalline conducting polymer. Transverse and longitudinal electrical conductivity with their frequency dispersion show marked difference. Its further investigation and applications are under progress.     

Synergetic effect of conducting polymer composites reinforced E-glass fabric for the control of electromagnetic radiations

The use of fibril materials as substrate for reinforcing polymers has wide industrial applications. In this article, we discuss polyaniline and polypyrrole as conducting polymers to provide electronic conductivity in E-glass fabric reinforced conducting composite with varied degree of composition and conductivity using industrially important polymers polymethylmethacrylate and polyvinyl chloride as a host matrix. Aromatic sulphonic acids such as PXSA, OXSA, PSA, PDSA, RDSA, OCPSA and MCSA were used as a dopant. The influence of the aromatic ring substituents in these dopants over the conductivity and processibility due to various interactions has been studied. The study shows that due to bulk nature of conductivity, shielding effectiveness (SE) increases with increase in conductivity and thickness of a composite. The test samples were characterized by conductivity and electromagnetic shielding effectiveness (EMI SE). The electromagnetic shielding effectiveness was measured by co-axial transmission line method in the frequency range of 0.01–1000 MHz. These composites with both side shielded by polypyrrole offered a uniform shielding effectiveness of 69 dB.     

Recent advances in thermoelectric materials

Thermoelectric materials are crucial in renewable energy conversion technologies to solve the global energy crisis. They have been proven to be suitable for high-end technological applications such as missiles and spacecraft. The thermoelectric performance of devices depends primarily on the type of materials used and their properties such as their Seebeck coefficient, electrical conductivity, thermal conductivity, and thermal stability. Classic inorganic materials have become important due to their enhanced thermoelectric responses compared with organic materials. In this review, we focus on the physical and chemical properties of various thermoelectric materials. Newly emerging materials such as carbon nanomaterials, electronically conducting polymers, and their nanocomposites are also briefly discussed. Strategies for improving the thermoelectric performance of materials are proposed, along with an insight into semiconductor physics. Approaches such as nanostructuring, nanocomposites, and doping are found to enhance thermoelectric responses by simultaneously tuning various properties within a material. A recent trend in thermoelectric research shows that high-performance thermoelectric materials such as inorganic materials and carbon nanomaterials/electronically conducting polymer nanocomposites may be suitable for power generation and energy sustainability in the near future.     

Charge Transfer in Fullerene-Conducting Polymer Compositex: Electronic and Excitonic Properties

C₆₀ doping into conducting polymer with highly extended π-electron system in the main chain induces remarkable quenching of photoluminescence in conducting polymer and drastic enhancement of photoconductivity. These results can be explained in terms of photo-induced charge transfer between conducting polymer and C₆₀. That is, photoexcited excitons or exciton-polarons on conducting polymer are effectively dissociated at C₆₀ molecules transferring electrons to C₆₀. Photoexcitation of C₆₀ results in the transfer of hole from C₆₀ to conducting polymer. These novel C₆₀ doping effects have been observed not only in conducting polymers with non-degenerated ground state structures but also those with degenerated ground state structure such as di-substituted acetylene polymers with solitonic electronic systems.

Highly effective photo-induced charge transfer has been also observed in conducting polymer/C₆₀ heterojunctions, which are interpreted as donor (D)-acceptor (A) photocell. Based on this finding we have demonstrated an organic photovoltaic cell with D-A double heterojunction, Al/C₆₀/OEP/conducting polymer/TTO, in which OEP is octaethylporphine as an light absorbing antenna molecule. Novel characteristics have also been observed in various other junction devices utilizing C₆₀ doped conducting polymer.

Granular and multiphase superconductivity has been found in C₆₀-conducting polymer-alkali metal composites.

Effect of other type of fullerenes such as C₇₀, modified C₆₀ and C₆₀ polymers, and also effect of C₆₀ doping in polysilanes and their derivatives have also been studied.     

Resolving Sub‐Molecular Binding and Electrical Switching Mechanisms of Single Proteins at Electroactive Conducting Polymers

Polymer‐based electrodes for interfacing biological tissues are becoming increasingly sophisticated. Their many functions place them at the cross‐roads of electromaterials, biomaterials, and drug‐delivery systems. For conducting polymers, the mechanism of conductivity requires doping with anionic molecules such as extracellular matrix molecules, a process that distinguishes them as biomaterials and provides a means to control interactions at the cellular–electrode interface. However, due to their complex structure, directly observing the selective binding of target molecules or proteins has so far eluded researchers. This situation is compounded by the polymer's ability to adopt different electronic states that alter the polymer–dopant interactions. Here, the ability to resolve sub‐molecular binding specificity between sulfate and carboxyl groups of dopants and heparin binding domains of human plasma fibronectin is demonstrated. The interaction exploits a form of biological ‘charge complementarity’ to enable specificity. When an electrical signal is applied to the polymer, the specific interaction is switched to a non‐specific, high‐affinity binding state that can be reversibly controlled using electrochemical processes. Both the specific and non‐specific interactions are integral for controlling protein conformation and dynamics. These details, which represent the first direct measurement of biomolecular recognition between a single protein and any type of organic conductor, give new molecular insight into controlling cellular interactions on these polymer surfaces.     

Influence of copolymer composition on the transport properties of conducting copolymers: poly(aniline-co-o-anisidine)

The effect of different compositions of monomers on the transport properties of copolymers by various techniques such as optical, electrical and magnetic has been investigated and compared with the homopolymers. The UV-visible absorption spectra show a hypsochromic shift with an increase in the o-anisidine content in copolymers indicating a decrease in the extent for conjugation (i.e. an increase in the bandgap). From temperature dependence of electrical conductivity the transport parameters such as charge localization length and average hopping distance are calculated and also the effect of the monomeric composition on the coherence length has been discussed. The magnetic studies show the paramagnetic and diamagnetic nature of homopolymers and copolymers. The X-ray diffraction pattern indicates that the copolymers are of amorphous nature.     

Conducting Polymers with Confined Dimensions: Track‐Etch Membranes for Amperometric Biosensor Applications

Organic conducting polymers can be synthesized inside the pores of a track‐etch membrane, and the resulting hollow tubules are shown to have enhanced electrical properties compared to their corresponding bulk materials. The polymerization of monomers (e.g., pyrrole, thiophenes) inside the confined space of these pores, combined with electrostatic interaction, ensures the alignment of the organic polymers on the interior, leading to higher conductivity. The application of these conducting tubes in the development of amperometric glucose sensors is discussed. Due to the special properties of conducting polymers inside a track‐etch membrane, biosensors with a unique electron‐transfer mechanism have been developed.     

Nanowired three-dimensional cardiac patches

Engineered cardiac patches for treating damaged heart tissues after a heart attack are normally produced by seeding heart cells within three-dimensional porous biomaterial scaffolds. These biomaterials, which are usually made of either biological polymers such as alginate or synthetic polymers such as poly(lactic acid) (PLA), help cells organize into functioning tissues, but poor conductivity of these materials limits the ability of the patch to contract strongly as a unit. Here, we show that incorporating gold nanowires within alginate scaffolds can bridge the electrically resistant pore walls of alginate and improve electrical communication between adjacent cardiac cells. Tissues grown on these composite matrices were thicker and better aligned than those grown on pristine alginate and when electrically stimulated, the cells in these tissues contracted synchronously. Furthermore, higher levels of the proteins involved in muscle contraction and electrical coupling are detected in the composite matrices. It is expected that the integration of conducting nanowires within three-dimensional scaffolds may improve the therapeutic value of current cardiac patches.     

Effect of different carbon fillers and dopant acids on electrical properties of polyaniline nanocomposites

Electrically conducting nanocomposites of polyaniline (PANI) with carbon-based fillers have evinced considerable interest for various applications such as rechargeable batteries, microelectronics, sensors, electrochromic displays and light-emitting and photovoltaic devices. The nature of both the carbon filler and the dopant acid can significantly influence the conductivity of these nanocomposites. This paper describes the effects of carbon fillers like carbon black (CB), graphite (GR) and muti-walled carbon nanotubes (MWCNT) and of dopant acids like methane sulfonic acid (MSA), camphor sulfonic acid (CSA), hydrochloric acid (HCl) and sulfuric acid (H₂SO₄) on the electrical conductivity of PANI. The morphological, structural and electrical properties of neat PANI and carbon–PANI nanocomposites were studied using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR), UV–Vis spectroscopy and the four-point probe technique, respectively. Thermogravimetric analysis (TGA) and X-ray diffraction (XRD) studies were also conducted for different PANI composites. The results show that PANI and carbon–PANI composites with organic acid dopants show good thermal stability and higher electrical conductivity than those with inorganic acid dopants. Also, carbon–PANI composites generally show higher electrical conductivity than neat PANI, with highest conductivities for PANI–CNT composites. Thus, in essence, PANI–CNT composites prepared using organic acid dopants are most suitable for conducting applications.     

Polymer Nanofibers and Nanotubes: Charge Transport and Device Applications

A critical analysis of recent advances in the synthesis and electrical characterization of nanofibers and nanotubes made of different conjugated polymers is presented. The applicability of various theoretical models is considered in order to explain results on transport in conducting polymer nanofibers and nanotubes. The relationship between these results and the one‐dimensional (1D) nature of the conjugated polymers is discussed in light of theories for tunneling in 1D conductors (e.g., Luttinger liquid, Wigner crystal). The prospects for nanoelectronic applications of polymer fibers and tubes as wires, nanoscale field‐effect transistors (nanoFETs), and in other applications are analyzed.     

Electrical conductivity of polyethylene-carbon-fibre composites mixed with carbon black

The study of electrical conductivity of high-density polyethylene-carbon-fibre composites mixed with different concentrations of carbon black is reported. The influence of the mixing procedure of the additives and material preparation is examined with regard to the conductivity values. The use of these two filler types in polyethylene composites combines the conducting features of both. Thus, while fibres provide charge transport over large distances (several millimetres), carbon black particles improve the interfibre contacts. Results are discussed with reference to simple electrical models. It is shown that for composites in which the segregated carbon black-polyethylene component lies above the percolation threshold the electrical interfibre contacts are activated through carbon black particle bridges, leading to a conductivity rise. This effect is more relevant in the case of shorter fibres. Processing of the material involving fibre orientation, such as in injection-moulding, decreases drastically the conductivity level reached.     

Patterning of conjugated polymers for organic optoelectronic devices

Conjugated polymers have been attracting more and more attention because they possess various novel electrical, magnetical, and optical properties, which render them useful in modern organic optoelectronic devices. Due to their organic nature, conjugated polymers are light-weight and can be fabricated into flexible appliances. Significant research efforts have been devoted to developing new organic materials to make them competitive with their conventional inorganic counterparts. It is foreseeable that when large-scale industrial manufacture of the devices made from organic conjugated polymers is feasible, they would be much cheaper and have more functions. On one hand, in order to improve the performance of organic optoelectronic devices, it is essential to tune their surface morphologies by techniques such as patterning. On the other hand, patterning is the routine requirement for device processing. In this review, the recent progress in the patterning of conjugated polymers for high-performance optoelectronic devices is summarized. Patterning based on the bottom-up and top-down methods are introduced. Emerging new patterning strategies and future trends for conventional patterning techniques are discussed.     

A combined nonequilibrium Green’s function/density-functional theory study of electrical conducting properties of artificial DNA duplexes

DNA duplexes have attracted much attention as a primary candidate for nanowires possessing self-organizing capability. To employ DNA duplexes as nanowires, however, a major drawback must be overcome; the guanine bases undergo oxidative degradation in a hole transport through DNA duplexes, which is likely caused by the presence of adjoining adenine bases that do not effectively mediate the charge transport through DNA duplexes. To overcome the drawback, several artificial nucleobases based on adenine have been designed and tested, confirming that the artificial nucleobase-containing DNA duplexes do not suffer from such an oxidative damage and exhibit high efficiency in hole transport through the DNA duplexes. In the present study, we examine the electrical conducting properties of these artificial DNA duplexes by use of nonequilibrium Green’s function and density-functional theory methods. The results explicate the origin of the experimentally observed high conductivity through the DNA duplexes containing the artificial DNA bases. We also put forth a computer-aided design of novel artificial DNA bases with low ionization energies, and examine the electrical conductivity of the DNA duplexes containing the designer nucleobases for potential use as highly conductive nanowires.     

A 2D Titanium Carbide MXene Flexible Electrode for High-Efficiency Light-Emitting Diodes

Although several transparent conducting materials such as carbon nanotubes, graphene, and conducting polymers have been intensively explored as flexible electrodes in optoelectronic devices, their insufficient electrical conductivity, low work function, and complicated electrode fabrication processes have limited their practical use. Herein, a 2D titanium carbide (Ti₃C₂) MXene film with transparent conducting electrode (TCE) properties, including high electrical conductivity (≈11 670 S cm⁻¹) and high work function (≈5.1 eV), which are achieved by combining a simple solution processing with modulation of surface composition, is described. A chemical neutralization strategy of a conducting-polymer hole-injection layer is used to prevent detrimental surface oxidation and resulting degradation of the electrode film. Use of the MXene electrode in an organic light-emitting diode leads to a current efficiency of ≈102.0 cd A⁻¹ and an external quantum efficiency of ≈28.5% ph/el, which agree well with the theoretical maximum values from optical simulations. The results demonstrate the strong potential of MXene as a solution-processable electrode in optoelectronic devices and provide a guideline for use of MXenes as TCEs in low-cost flexible optoelectronic devices.     

Theoretical approaches to superionic conductivity

Recent theoretical approaches to the understanding of superionic conductivity in polycrystalline, glassy and polymeric materials are briefly reviewed. Phase transitions to the superionic conducting state in the AgI family are apparently triggered by cluster formation and strong mobile ion interaction within the clusters. Anomalous conductivity and related physical properties are explained in the cluster induced distortion model. Ionic composites such as AgX : Al₂O₃ (X = Cl, Br and I) involve conducting and non-conducting phases and the all-important interface between the two whose space charge enhances the conductivity and also trigger phase transitions to exotic polymorphic phases, for which the mechanisms are yet to be explored. Ion hopping dynamics controls the conductivity of superionic glasses. Mode coupling and jump relaxation theories account for the non-Debye relaxation observed in a.c. conductivity of these glasses. The theory of conductivity in polymer electrolytes—still in its infancy—involves their complex structure and glass transition behaviour. Preparative and thermal history, composition and crystallinity control ionic conductivity. New approaches to the synthesis of optimal polymer electrolytes such as rubbery electrolytes, crystalline polymers and nanocomposites must be considered before achieving a comprehensive theoretical understanding. Based on an invited talk given by the first author at the National Workshop on Solid State Ionics and its Applications, Bharatiar University, Coimbatore, 18–23 January 2002.