Unified Hamiltonian for conducting polymers

Two transferable physical parameters are incorporated into the Su-Schrieffer-Heeger Hamiltonian to model conducting polymers beyond polyacetylene: the parameter γ scales the electron-phonon coupling strength in aromatic rings and the other parameter ε specifies the heterogeneous core charges. This generic Hamiltonian predicts the fundamental band gaps of polythiophene, polypyrrole, polyfuran, poly-(p-phenylene), poly-(p-phenylene vinylene), and polyacenes, and their oligomers of all lengths, with an accuracy exceeding time-dependent density functional theory. Its computational costs for moderate-length polymer chains are more than eight orders of magnitude lower than first-principles approaches.     

Prospects of conducting polymers in molecular electronics

Molecular electronics (ME) is rapidly evolving from physics, chemistry, biology, electronics and information technology. This is because the present-day advanced silicon chip can store about 16 million bytes of information within an area less than 1 cm². Organic materials such as proteins, pigments and conducting polymers (CPs) have been considered as alternatives for carrying out the same functions that are presently being performed by semiconductor silicon. Among these, CPs have demanded the maximum attention. These ME materials differ from conventional polymers by having a delocalized electronic structure that can accommodate charge carriers such as electrons and holes. Besides, these conjugated electronic materials exhibit Peierl’s instabilities due to built-in highly anisotropic interactions. It has been proposed that electrical conduction in CPs occurs via non-linear (or topological) defects (solitons/polarons) generated either during polymerization or as a consequence of doping. Solitons and polarons have recently been shown to have implications in the technical development of ME devices.CPs such as polypyrroles, polythiophenes and polyanilines have been projected for applications for a wide range of ME devices. One of the main reasons for such a wide-spread interest is due to the reported observation that these interesting electronic materials exhibit full range of properties from insulator to superconductor depending upon chemical modification. CPs have been found to have applications as optical, electronic, drug-delivery, memory and biosensing devices. The major challenge confronting the material scientists including chemists and physicists is how do the properties of these electronic materials differ from those of conventional semiconductors. Another advantage lies in the fact that these materials possess specific advantages such as high packing density, possibility of controlling shape and electronic properties by chemical modification.Our group has been actively working towards the application of CPs to Schottky diodes, metal–insulator–semiconductor devices and biosensors for the past about 10 years. This paper is a review of some of the results obtained at our laboratory in the area of CP ME.     

Metallic solutions of the continuum model for conducting polymers

In the continuum approximation of the Su-Schrieffer-Heeger model for degenerate and nondegenerate ground state systems, an exhaustive survey of solutions of the standard gap equations is given. With special emphasis on the electronic energy spectrum, the pertinent results of Takahashi [1] are extended to the whole μ, k-plane. Periodic metallic phases and their grand potentials are discussed.     

Laser induced forward transfer of conducting polymers

We report on laser printing of conducting polymers directly from the solid phase. Laser induced forward transfer is employed to deposit P3HT:PCBM films on glass/ITO/PEDOT:PSS substrates. P3HT:PCBM is widely used as the active material in organic solar cells. Polyaniline films, which are also printed by laser induced forward transfer, find many applications in the field of biotechnology. Laser printing parameters are optimized and results are presented. To apply solid-phase laser printing, P3HT:PCBM films are spun cast on quartz substrates, while aniline is in-situ polymerized on quartz substrates.     

One-electron Hamiltonian matrix elements in conducting polymers

The Wannier function method used in a stable lattice is extended to calculate one-electron Hamiltonian matrix elements in polyacetylene. In this technique only a2P _z orbital of the electrons is taken into account and the matrix elements are given analytically, to show the electronic contribution to the nonneighbor hopping.     

Interaction-created effective flat bands in conducting polymers

For a general class of conducting polymers with arbitrary large unit cell and different on-site Coulomb repulsion values on different type of sites, I demonstrate in exact terms the emergence possibility of an upper, interaction-created “effective” flat band. This last appears as a consequence of a kinetic energy quench accompanied by a strong interaction energy decrease, and leads to a non-saturated ferromagnetic state. This ordered state clearly differs from the known flat-band ferromagnetism. This is because it emerges in a system without bare flat bands, requires inhomogeneous on-site Coulomb repulsions values, and possesses non-zero lower interaction limits at the emergence of the ordered phase.     

高压下某些导电高分子色散关系的研究

利用晶格动力学方法,研究在高压下几种导电高分子具有不同晶格链时的色散关系及其曲线的变化.链间耦合作用的减弱使横波与纵波的ω差值相应增大,且在BZ边界处拉开一个间隙,这是维度作用的结果.     

Spin dynamics in conducting polymers studied by μSR

We report studies of spin dynamics in the conducting polymers polyaniline and polypyrrole using both μ⁺SR and μ^-SR techniques. These measurements reveal characteristic field dependences and cutoff frequencies for the muon spin relaxation which can be related to the spin diffusion process. Clear evidence is seen for increased spin localisation at low temperatures where a crossover occurs from two or three dimensional spin diffusion to a one dimensional diffusion regime. This revised version was published online in August 2006 with corrections to the Cover Date.     

Transparent conducting hybrid thin films fabricated by layer-by-layer assembly of single-wall carbon nanotubes and conducting polymers

The effect of conducting polymers on the performance of transparent conducting SWNT thin films fabricated by the layer-by-layer (LBL) assembly has been investigated. Transparent conducting SWNT thin films were fabricated by the LBL assembly in two ways, one using conducting polymers, PEDOT-PEG, and the other using non-conducting polymers, PAH, and their electrical and optical properties were compared. The sheet resistance of (PSS-SWNT/PEDOT-PEG) _n films is more than thrice lower than that of (PSS-SWNT/PAH) _n films for the same n while the decrease of optical transmittance due to the absorbance of PEDOT-PEG is fairly small (ca. 2?% at n=30). The conductivity ratio of the (PSS-SWNT/PEDOT-PEG)₃₀ is 3.3 times larger than that of the (PSS-SWNT/PAH)₃₀. These figures indicate that the performance of the transparent conducting SWNT thin films fabricated by the LBL assembly is highly improved by using conducting polymers instead of non-conducting ones.     

MnO2-polypyrrole conducting polymer composite electrodes for electrochemical redox supercapacitors

Redox supercapacitors using electrochemically synthesised MnO₂-polypyrrole composite electrodes have been fabricated with different electrolytes, namely polymer electrolyte film (polyvinyl alcohol, PVA-H₃PO₄ aqueous blend), aprotic liquid electrolyte (LiClO₄-propylene carbonate, PC) and polymeric gel electrolyte [poly methyl methacrylate, (PMMA)-Ethylene carbonate (EC)-Propylene carbonate (PC)-NaClO₄]. The capacitors have been characterised using galvanostatic charge-discharge methods. The cell with aqueous PVA-H₃PO₄ shows non-capacitive behaviour owing to some reversible chemical reaction of MnO₂ with water while the MnO₂-polypyrrole composite is found to be a suitable electrode material for redox supercapacitors with aprotic (non-aqueous) electrolytes. The solid state supercapacitor based on MnO₂-polypyrrole composite electrodes with gel electrolyte gives stable values of capacitance of 10.0–18.0 mF cm⁻² for different discharge current densities.     

Surface excitation correction of the inelastic mean free path in selected conducting polymers

In earlier works, the inelastic mean free path (IMFP) of electrons was determined by elastic peak electron spectroscopy (EPES) using Ni and Ag reference standard samples, but fully neglecting surface excitation. Surface excitation that is characterized by the surface excitation parameter (SEP), and may affect considerably the elastic peak for the sample and the reference material. The SEP parameters of selected conducting polymers (polythiophenes, polyaniline and polyethylene) were determined by EPES using Si and Ge reference samples. Experiments were made with a hemispherical analyzer of energy resolution 100-200 meV in the E = 0.2-2.0 keV energy range. The composition of the sample surfaces was determined by in situ XPS, their surface roughness by AFM. The experimental SEP parameter data of eight polymer samples were determined by our new procedure, using the formulae of Chen and Werner et al. in the E = 0.2-2.0 keV energy range. The trial and error procedure is based on the best approach between the experimental and calculated IMFPs, corrected on surface excitation. The improvement in the SEP correction appears in the difference between the corrected and Monte Carlo calculated IMFPs, assuming Gries and Tanuma et al. IMFPs for polymers and standard, respectively. The term describing the improvement by SEP resulted in 50-72% (good correction for five polymers) 24% (poor correction for one polymer), 1-6% (no correction for two polymers). The 100% correction was not achieved, indicating that the difference between experimental and calculated IMFP cannot be entirely explained by surface excitation. Using the SEP data of Si and Ge reference samples based on Chen's and Werner's material parameter values resulted in similar SEP corrections for the polymer samples.