Nonlinear transport and localization in single-walled carbon nanotubes

We have measured the electrical transport properties of mats of single-walled carbon nanotubes (SWNT) as a function of applied electric and magnetic fields. We find that at low temperatures the resistance as a function of temperature R(T) follows the Mott variable range hopping (VRH) formula for hopping in three dimensions. Measurement of the electric field dependence of the resistance R(E) allows for the determination of the Bohr radius of a localized state a = 700nm. The magnetoresistance (MR) of SWNT mat samples is large and negative at all temperatures and fields studied. The low field negative MR is proportional to H2, in agreement with variable range hopping in two or three dimensions. 3D VRH indicates good intertube contacts, implying that the localization is due to the disorder experienced by the individual tubes. The 3D localization radius gives a measure of the ID localization length on the individual tubes, which we estimate to be >700 nm. Implications for the electron-phonon mean free path are discussed.

Electrochemical synthesis and characterization of conducting polymers using room temperature melt as an electrolyte

Aromatic monomers can be polymerised using the chloroaluminate room temperature melt obtained by mixing 1:2 ratio of cetyl pyridinium chloride and anhydrous aluminium chloride miscible in all proportions with organic solvents as an electrolyte. The chloroaluminate (AlCl4-) anion generated in this melt having a tetrahedral symmetry with equal bond lengths and bond angles is the dopant to stabilize macrocation generated near the vicinity of anode to yield better conducting and better ordered electronically conducting free standing polymer film. In this communication, we discuss the polymers derived from benzene and pyrrole and their characterization by various techniques.

A new route to synthesize high degree polythiophene in a room temperature melt medium

Conducting polymers suffer from folds and kinks because of random nucleation and solvation of a free radical cation to yield a cross linked/disordered polymer and therefore a solvent free electrochemical polymerization in a room temperature melt medium is adopted to yield a high degree polymer with high electronic conductivity. Electropolymerization of thiophene was performed on platinum/ITO substrates using cyclic voltametry or galvenostatic mode in chloroaluminate room temperature melt medium to obtain a reddish brown free standing film which can be peeled off from the electrode surface after a minimum of 10 cycles. The conductivity was found to be around 102 S/cm. The degree of polymerization was calculated to be around 44 from IR studies. A layered structure supportive for high degree of polymerization was witnessed from potential step technique. From UV spectra the charge carriers were found to be bipolarons. The morphology of the film was found to be crystalline from SEM and XRD studies. Capacitative impedance properties for doped samples were interpreted from impedance spectroscopy.

Electrochemical synthesis and characterization of conducting polyparaphenylene using room-temperature melt as the electrolyte

Freestanding polyparaphenylene films were obtained on polymerization of benzene at potential of 1.2 V versus Al wire on substrates like platinum/transparent conducting glass as an anode. The electrolyte used was chloroaluminate room-temperature melt, which was prepared by intimate mixing of a 1:2 ratio of cetyl pyridinium chloride and anhydrous aluminum chloride to yield a viscous liquid. This liquid was miscible in all proportions with benzene and other aromatic hydrocarbons in all proportions at room temperature. The polyparaphenylene films deposited on platinum anode exhibited a prominent cyclic voltammetric peak at 0.7 V versus Al wire as reference electrode in chloroaluminate medium. The impedance spectra gave low charge transfer resistance. The diffused reflectance electronic spectra of the film gave the peaks at 386 nm and 886 nm. The PPP films showed electronic conductivity around 3–4 × 104 S/cm by four probe method under nitrogen atmosphere. The polymer was also characterized by IR spectra, thermal studies, and SEM studies.

Plasma Polymerised Organic Thin Films-A Study on the Structural, Electrical and Nonlinear Optical Properties for Possible Applications

This proposed thesis is entitled “Plasma Polymerised Organic Thin Films: A study on the Structural, Electrical, and Nonlinear Optical Properties for Possible Applications. Polymers and polymer based materials find enormous applications in the realm of electronics and optoelectronics. They are employed as both active and passive components in making various devices. Enormous research activities are going on in this area for the last three decades or so, and many useful contributions are made quite accidentally. Conducting polymers is such a discovery, and eversince the discovery of conducting polyacetylene, a new branch of science itself has emerged in the form of synthetic metals. Conducting polymers are useful materials for many applications like polymer displays, high density data storage, polymer FETs, polymer LEDs, photo voltaic devices and electrochemical cells. With the emergence of molecular electronics and its potential in finding useful applications, organic thin films are receiving an unusual attention by scientists and engineers alike. This is evident from the vast literature pertaining to this field appearing in various journals. Recently, computer aided design of organic molecules have added further impetus to the ongoing research activities in this area. Polymers, especially, conducting polymers can be prepared both in the bulk and in the thinfilm form. However, many applications necessitate that they are grown in the thin film form either as free standing or on appropriate substrates. As far as their bulk counterparts are concerned, they can be prepared by various polymerisation techniques such as chemical routes and electrochemical means. A survey of the literature reveals that polymers like polyaniline, polypyrrole, polythiophene, have been investigated with a view to studying their structural electrical and optical properties. Among the various alternate techniques employed for the preparation of polymer thin films, the method of plasma polymerisation needs special attention in this context. The technique of plasma polymerisation is an inexpensive method and often requires very less infra structure. This method includes the employment of ac, rf, dc, microwave and pulsed sources. They produce pinhole free homogeneous films on appropriate substrates under controlled conditions. In conventional plasma polymerisation set up, the monomer is fed into an evacuated chamber and an ac/rf/dc/ w/pulsed discharge is created which enables the monomer species to dissociate, leading to the formation of polymer thin films. However, it has been found that the structure and hence the properties exhibited by plasma polymerized thin films are quite different from that of their counterparts produced by other thin film preparation techniques such as electrochemical deposition or spin coating. The properties of these thin films can be tuned only if the interrelationship between the structure and other properties are understood from a fundamental point of view. So very often, a through evaluation of the various properties is a pre-requisite for tailoring the properties of the thin films for applications. It has been found that conjugation is a necessary condition for enhancing the conductivity of polymer thin films. RF technique of plasma polymerisation is an excellent tool to induce conjugation and this modifies the electrical properties too. Both oxidative and reductive doping can be employed to modify the electrical properties of the polymer thin films for various applications. This is where organic thin films based on polymers scored over inorganic thin films, where in large area devices can be fabricated with organic semiconductors which is difficult to achieve by inorganic materials. For such applications, a variety of polymers have been synthesized such as polyaniline, polythiophene, polypyrrole etc. There are newer polymers added to this family every now and then. There are many virgin areas where plasma polymers are yet to make a foray namely low-k dielectrics or as potential nonlinear optical materials such as optical limiters. There are also many materials which are not been prepared by the method of plasma polymerisation. Some of the materials which are not been dealt with are phenyl hydrazine and tea tree oil. The advantage of employing organic extracts like tea tree oil monomers as precursors for making plasma polymers is that there can be value addition to the already existing uses and possibility exists in converting them to electronic grade materials, especially semiconductors and optically active materials for photonic applications. One of the major motivations of this study is to synthesize plasma polymer thin films based on aniline, phenyl hydrazine, pyrrole, tea tree oil and eucalyptus oil by employing both rf and ac plasma polymerisation techniques. This will be carried out with the objective of growing thin films on various substrates such as glass, quartz and indium tin oxide (ITO) coated glass. There are various properties namely structural, electrical, dielectric permittivity, nonlinear optical properties which are to be evaluated to establish the relationship with the structure and the other properties. Special emphasis will be laid in evaluating the optical parameters like refractive index (n), extinction coefficient (k), the real and imaginary components of dielectric constant and the optical transition energies of the polymer thin films from the spectroscopic ellipsometric studies. Apart from evaluating these physical constants, it is also possible to predict whether a material exhibit nonlinear optical properties by ellipsometric investigations. So further studies using open aperture z-scan technique in order to evaluate the nonlinear optical properties of a few selected samples which are potential nonlinear optical materials is another objective of the present study. It will be another endeavour to offer an appropriate explanation for the nonlinear optical properties displayed by these films. Doping of plasma polymers is found to modify both the electrical conductivity and optical properties. Iodine is found to modify the properties of the polymer thin films. However insitu iodine doping is tricky and the film often looses its stability because of the escape of iodine. An appropriate insitu technique of doping will be developed to dope iodine in to the plasma polymerized thin films. Doping of polymer thin films with iodine results in improved and modified optical and electrical properties. However it requires tools like FTIR and UV-Vis-NIR spectroscopy to elucidate the structural and optical modifications imparted to the polymer films. This will be attempted here to establish the role of iodine in the modification of the properties exhibited by the films

Nanosecond optical limiting response of sandwich-type neodymium dyphthalocyanine in a co-polymer host

The nanosecond optical limiting characteristics of sandwich-type neodymium diphthalocyanine in a co-polymer matrix of polymethyl methacrylate (PMMA) and methyl-2-cyanoacrylate have been studied for the first time. The measurements were performed using 9 ns laser pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The optical limiting performance of neodymium diphthalocyanine in co-polymer host was studied at different linear transmission. Laser damage threshold was also measured for the doped and undoped co-polymer samples. The optical limiting response is attributed to reverse saturable absorption which is due to excited-state absorption.

Photoluminescence studies on RF plasma-polymerized thin films

Conjugated polymers in the form of thin films play an important role in the field of materials science due to their interesting properties. Polymer thin films find extensive applications in the fabrication of devices, such as light emitting devices, rechargeable batteries, super capacitors, and are used as intermetallic dielectrics and EMI shieldings. Polymer thin films prepared by plasma-polymerization are highly cross-linked, pinhole free, and their permittivity lie in the ultra low k-regime. Electronic and photonic applications of plasma-polymerized thin films attracted the attention of various researchers. Modification of polymer thin films by swift heavy ions is well established and ion irradiation of polymers can induce irreversible changes in their structural, electrical, and optical properties. Polyaniline and polyfurfural thin films prepared by RF plasmapolymerization were irradiated with 92MeV silicon ions for various fluences of 1×1011 ions cm−2, 1×1012 ions cm−2, and 1×1013 ions cm−2. FTIR have been recorded on the pristine and silicon ion irradiated polymer thin films for structural evaluation. Photoluminescence (PL) spectra were recorded for RF plasma-polymerized thin film samples before and after irradiation. In this paper the effect of swift heavy ions on the structural and photoluminescence spectra of plasma-polymerized thin films are investigated.

Structure property relationships in electrically conducting copolymers formed from pyrrole and N-methyl pyrrole

A series of copolymers containing differing proportions of pyrrole and N-methyl pyrrole were prepared electrochemically at various temperatures using acetonitrile as the solvent. The resultant electrical conductivity decreases universally with increasing fraction of N-methyl pyrrole. Films prepared with p-toluene sulfonate as the dopant show a marked variation in structural anisotropy as revealed by X-ray scattering with apparent copolymer content. There is a clear trend between the variation in electrical conductivity and this structural anisotropy. Different patterns of behaviour are observed for films prepared using perchlorate as the dopant and this is attributed to the role of the dopant and final structure in determining the relative reactivities of the pyrrole and N-methyl pyrrole monomers. These observations support the concept that the introduction of methyl substituents into a polypyrrole chain results in a twisted chain conformation. The structure and properties of the resultant copolymer films are particularly sensitive to the preparation conditions.

The effect of dopant molecules on the molecular order of electrically-conducting films of polypyrrole

X-ray scattering curves have been measured for a range of electrochemically-prepared conducting polypyrrole films employing a variety of counterions in aqueous solutions. Films containing counterions based on aromatic rings exhibit an anisotropic molecular organization. The degree of anisotropy is enhanced through the use of highly planar counterions. The electrical conductivity of such films is also improved if the charge/volume ratio of the counterion is maintained at a high level. Polypyrrole films prepared using ‘spherically’ shaped counterions such as SO42− do not display such anisotropic molecular organizations, and exhibit lower electrical conductivities. The competing structural roles of the counterions within these molecular composites are discussed.

Effects of torsional disorder on poly-para-phenylene

We study the effect of thermal disorder on the electronic structure of one-dimensional poly-para-phenylene (PPP). In a real chain the torsion angles between rings are bound to be distributed over a range of values, which depend on temperature, and thus the chain is intrinsically disordered. In this study we simulated this kind of thermally induced off-diagonal disorder through the simple Huckel method. We base our Hamiltonian on ab initio results for the effect of temperature on torsion angles, and the effect of torsion angles on the energy gap. We analyze the electronic structure of 200-monomer-long chains focusing on the density of states, and the associated localization character (measured by the inverse participation ratio). Our results contrast with the usually assumed Gaussian-shaped density of localized states for disordered systems. (C) 2009 Elsevier B.V. All rights reserved.

Classical simulation of deposition of thiophene oligomers on TiO(2)-anatase: Relevance of long-range electrostatic interactions

We performed classical molecular dynamics simulations of the vapor-deposition of alpha-T4 oligomers on the TiO(2)-anatase (101) surface, comparing different sets of charges associated with the atoms of the model. The potential energy surfaces for alpha-T4 and TiO(2) were described by re-parametrizations of the Universal force field with charges given by the charge equilibration (QEq) scheme, or with fixed charges obtained by an ab initio method using the Hirshfeld partition. The two sets of charges lead to completely different results for the interface formation, and for the characteristics of the organic film, with a clearly defined alpha-T4 contact layer in the QEq case, and a more homogeneous molecular distribution when using Hirshfeld charges. The main reason for the discrepancy was found to be the incorrect charge assignment given by QEq to the sulfur and alpha-carbon atoms in thiophenes, and highlight the relevance of long-range interactions in the organization of molecular films. (C) 2009 Elsevier B.V. All rights reserved.

Photoluminescence of MEH-PPV with ultraviolet excitation

The basic optical properties of PPV-based polymers have been extensively studied due to their potential technological applications. However, a detailed investigation of electronic processes following photoexcitation in the ultraviolet is still lacking. We report photoluminescence measurements on poly(1-methoxy-4-ethylhexyloxy-paraphenylenevinylene) - MEH-PPV in the 2.0-5.6 eV range, with excitation up to 5.6 eV. The photoluminescence spectra lineshape is independent of excitation energy. The photoluminescence efficiency is high for energies well below the absorption maximum due to near-resonant excitation of the longest conjugated segments which are responsible for the PL It decreases strongly for excitation energies in the range 2.1-2.5 eV (up to the absorption maximum) and slightly from 2.5 to 5.6 eV. The results indicate that states excited in the ultraviolet rapidly relax nonradiatively to the lowest state, from where the usual luminescence occurs. (C) 2010 Elsevier B.V. All rights reserved.

Detection of microwaves using the organic semiconductor poly(p-phenylenevinylene)

We report a new procedure to convert the polymer precursor poly(xylylidene tetrahydrothiophenium chloride) (PTHT) into poly(p-phenylenevinylene) (PPV) using microwave irradiation. Spin-coated PTHT films were irradiated at room temperature under ambient conditions in a commercial microwave oven, with varying power from 20W to 100W. Complete conversion was reached within only 5 min of irradiation for powers above 50W, yielding PPV films with absorption and photoluminescence spectra that are practically indistinguishable from the spectra of thermally converted PPV films, which require ca. 2 h of a high temperature (similar to 200 degrees C) thermal treatment. In addition to a much faster conversion procedure, the irradiation with microwaves led to a red shift in the absorption spectrum of a PTHT film, which varied linearly with the time of irradiation. These films can then be used as low-cost, easy-to-use detectors of microwaves. (C) 2010 Elsevier B.V. All rights reserved.

Nitric oxide sensing by cytochrome c bonded to a conducting polymer modified glassy carbon electrode

A nitric oxide biosensor based on cytochrome c (an heme protein) covalently immobilized to poly(5-amino-1-naphthol) by using cyanuric chloride as a bridge was developed. The immobilization was studied by cyclic voltammetry and quartz crystal microbalance. The nitric oxide detection as a function of poly(5-amino-1-naphthol) amount was recorded, and the best result was obtained with the electrode prepared by 70 cycles. The sensitivity and detection limit were 0.015 mu A cm(-2)/mu mol L(-1) and 2.85 mu mol L(-1), respectively. (C) 2009 Elsevier B.V. All rights reserved.

On the energy transfer from a polymer host to the rhenium(I) complex in OLEDs

Photoluminescence and electroluminescence of PVK films doped with fac-[ClRe(CO)(3)(bpy)], bpy=2,2`-bipyridine, are investigated. Photoluminescence spectra of spin-coated PVK films (lambda(exc)=290 nm) exhibit a broad band centered at 405 nm. As the concentration of dopant increases, the polymer emission is quenched and a band at 555 nm appears (isosbestic point at 475 nm). In OLEDs with ITO/PEDOT:PSS/PVK/butylPBD/Al architecture doped with fac-[ClRe(CO)(3)(bpy)], the polymer host emission is completely quenched even at the lowest concentration of dopant. The electroluminescence spectra of the devices show that there is an efficient energy transfer from the host to the dopant, which exhibits a very intense emission at 580 nm. (C) 2009 Elsevier B.V. All rights reserved.