Electrical and Optical Properties of Conducting Polymer and Carbons in Nano-Scale Periodic Structure and their Intercalation Effects

Abstract

Nano-scale periodic structures of conducting polymer and carbons, which were prepared by infiltration of polymers and carbons in nano-scale interconnected periodic pores in synthetic opals made of regular array of SiO₂ spheres and then removing SiO₂ by etching, have been found to exhibit novel electrical and optical properties. Their electrical and optical properties in thus fabricated conducting polymer and carbon replicas change drastically upon pyrolysis due to progress of carbonization and graphitization. That is, due to the changes in periodicity, pore size, carbonization degree and crystal structure, electrical conductivity, magnetoconductance and their temperature dependences and optical reflection spectra have changed drastically. These replicas with porous nature can be infiltrated and also intercalated with various materials, resulting in also remarkable changes of properties. The synthetic opal infiltrated with conducting polymer can be electrochemically doped, with which remarkable change of optical properties have been observed due to the shift of the diffraction peak accompanying with the change in refractive index. Alkali metal intercalated carbon and graphite with nano-scale periodic structures have been also studied. The applications of these nano-scale periodic structures of conducting polymer and carbon are also discussed.     

Recent advances with electro-optic polymers

Abstract

In recent years the electro-optic polymers emerged as an important branch of material science. This growth and interest is fundamentally motivated by practical application of these materials in second-order nonlinear optics and in waveguiding configuration. Indeed, these materials marry excellent optical quality of amorphous σ bonded polymers with enhanced first hyperpolarizability of imbedded organic nonlinear optical molecules. Although a big progress was achieved with them, concerning particularly the science, understanding and applications, some problems remain still incompletely solved, particularly the stability of induced polar order by the application of external electric field and the molecule aggregation. In this review paper we recall techniques of thin film fabrication, poling, characterization of NLO properties and discuss more precisely problems of molecule aggregation as well as the temporal decay of polar order. A novel 3D second-order NLO chromophores, namely the [2] paracyclophanes, which may help to limit the aggregation, are proposed. We show, in particular, that this molecule can be poled in doped PMMA thin films. Practical applications of electro-optic polymers are also reviewed and discussed.     

Photochemical activities of polymers with aurone fragment

ABSTRACT

In this work we report preliminary results obtained for methacrylic polymers incorporating aurone side-group as photochemical active molecule. The aurone polymers were obtained by a three-step synthetic approach: (2Z)-6-hydroxy-2-(4-R-benzyliden)-1-benzofuran-3(2H)-ones were synthesized by using condensation reation of 6-hydroxybenzofuran-3-one with benzaldehydes; then methacrylate monomers were synthesized by reaction the alcohols with methacryloyl chloride; and the polymers were synthesized by free radical polymerization. Polymers were characterized by ¹HNMR spectroscopy and DSC techniques. Their physicochemical properties are determined by absorption, fluorescence excitation and emission spectroscopies.     

Synthesis of quinoxaline-based D-A type conjugated polymers for photovoltaic applications

Abstract

Two quinoxaline-based conjugated polymers were successfully synthesized for application in polymer solar cells (PSCs). The quinoxaline unit with an electron-donating dimethylamino substituent was used as the electron-accepting (A) moiety, whereas indacenodithiophene (IDT) and indacenodithieno-thiophene (IDTT) were chosen as the electron-donating (D) groups to synthesize D-A type conjugated polymers. To investigate the photovoltaic properties of the polymers, an inverted-type device with the configuration of ITO/ZnO/polymer:PC₇₁BM/MoO₃/Ag was fabricated. It has been observed that the overall performances of the organic photovoltaic cells were significantly improved by changing the electron-donating components from IDT to IDTT. Therefore, this study can provide insights into the design and structure–property correlation of quinoxaline-based conjugated polymers for PSCs.     

“Polyaniline”: Interconversion of Metallic and Insulating Forms

Abstract

“Polyaniline” has been synthesized in various forms both chemically and electrochemically in aqueous media. The qulnoid-benzenoid-diimine form, an insulator, is doped by dilute aqueous protonic acids to the metallic regime ([sgrave] = 5 ohm^?1cm^?1; compressed pellet) to give the corresponding iminium salt. This represents a new type of p-doping phenomenon in a conducting polymer. Both these forms are stable in the presence of air and/or water. The doping process is reversed by treatment with aqueous alkali. Cyclic voltammetry studies in an aqueous electrolyte show excellent reversibility between selected reduced and oxidized forms of polyaniline.     

Optical properties of azo-based poly(azomethine)s with aromatic fluorinated fragments,ether linkages and aliphatic units in the backbone

Abstract

The aim of this work is to study the optical properties of the core-fluorinated azo-containing polyazomethines with 1,4-tetrafluorobenzene or 4,4′-octafluorobiphenylene dioxyphenylene units and aliphatic fragments in the chain. Due to the reorganization process at the nanometer-scale under UV/Vis irradiation, azo-containing polymers (APs) have attracted much attention as materials for biology, optoelectronics, nano-manipulation field, etc. Moreover, the introduction of azomethine group into these polymers enhances not only their optical properties but also expands their practical application. APs polymers have the useful combination of chemical and physical properties such as liquid crystalline states, high nonlinearity and an ability to form metal complexes. It was shown that the optical properties of such polymers could be improved by the inclusion of fluorine. Fluorinated polymers demonstrate high thermal stability and have low dielectric constant and dielectric losses. It should be noted that the presence of flexible moieties in a polymer backbone allows regulating the different properties (solubility, thermostability, optical and liquid crystalline properties) of the final materials.     

Frequency Dependence of The Conductivity and Dielectric Constant of Ch(Ircl6) Y and Ch(I)Y

Abstract

We have measured the ac properties of polyacetylene doped with H2IrCl₆ 6H₂O and I₂ from 10⁵ to 10⁷ Hz at room temperature. We find in both cases that the conductivity is only weakly dependent on frequency, in agreement with previous work.^1,2 However, we find that the dielectric constant of CH(IrCl₆)_y is anomalously large ?10⁴. We suggest that the large dielectric constant can be modeled by an effective medium theory assuming that the CH(IrCl₆)_y is a mixture of conducting and insulating regions. TEM evidence in support of the model will be presented. The results of CH(IrCl₆)_y will be contrasted with CH(I)_y where TEM evidence shows a uniform distribution of dopant in the polyacetylene and the dielectric constant is significantly lower.     

Electrochemical characterizations and the effect of glycerol in biopolymer electrolytes based on methylcellulose-potato starch blend

ABSTRACT

Polymer electrolytes have been prepared by blending methylcellulose (MC)-potato starch, doped with lithium perchlorate (LiClO₄) and plasticized with glycerol. The blend of 60 wt% MC-40 wt% starch was found to be the most suitable ratio to serve as polymer host. Fourier transform infrared (FTIR) spectroscopy analysis proved the interaction among the components. X-ray diffraction (XRD) analysis indicated that the conductivity enhancement is due to the increase in amorphous content. The highest ionic conductivity obtained at room temperature was (4.25 ± 0.82) × 10^?4 S cm^?1 for MC-starch-LiClO₄-20 wt% glycerol. The highest conducting samples in both systems were found to obey Arrhenius rule. Dielectric study further strengthens the conductivity result.     

Studies on optical properties of polycrystalline SnO2:Sb thin films prepared using SnCl2 precursor

Optical properties of spray deposited antimony (Sb) doped tin oxide (SnO₂) thin films, prepared from SnCl₂ precursor, have been studied as a function of antimony doping concentration. The doping concentration was varied from 0‐4 wt.% of Sb. All the films were deposited on microscope glass slides at the optimized substrate temperature of 400 °C. The films are polycrystalline in nature with tetragonal crystal structure. The doped films are degenerate and n‐type conducting. The sheet resistance of tin oxide films was found to decrease from 38.22 Ω/□ for undoped films to 2.17 Ω/□ for antimony doped films. The lowest sheet resistance was achieved for 2 wt.% of Sb doping. To the best of our knowledge, this sheet resistance value is the lowest reported so far, for Sb doped films prepared from SnCl₂ precursor. The transmittance and reflectance spectra for the as‐deposited films were recorded in the wavelength range of 300 to 2500 nm. The transmittance of the films was observed to increase from 42 % to 55 % (at 800 nm) on initial addition of Sb and then it is decreased for higher level of antimony doping. This paper investigates the variation of optical and electrical properties of the as‐deposited films with Sb doping. (© 2003 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Growth and optical homogeneity investigations of Fe and Fe:Mn codoped LiNbO3 crystals

Lithium niobate (LiNbO₃) crystals doped with Fe and Fe:Mn were grown by Czochralski technique. The doping concentrations of Fe and Mn were optimized. Transmission studies reveal broad absorption band centered at 488 nm. The UV cutoff observed for Fe doped LiNbO₃ is 358 nm whereas for Fe:Mn codoped LiNbO₃ is 352 nm. This decrease in UV cutoff for Fe and Mn codoped LiNbO₃ compared to only Fe doped LiNbO₃ is due to the increase in Li/Nb ratio. Optical homogeneity was assessed using conoscopy and birefringence interferometry. Dark and photo conductivity measurements prove that LiNbO₃ is a negative photo conducting material. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis,structure, and mesomorphism of novel liquid crystalline acrylate monomers and polymers

A series of novel liquid crystalline monomers (M₁?M₈) and side chain polymers base polyacrylate backbone were synthesized. The chemical structures were characterized by FT-IR and ¹H-NMR spectra. The mesomorphism and thermal behavior was investigated by polarizing optical microscopy, differential scanning calorimetry, and thermogravimetric analysis. The relationships of structure and mesomorphism are discussed in detail. The eight monomers and their corresponding polymers all show enantiotropic nematic phase. With increasing the spacer length or flexibility of the terminal group, the melting temperature (T_m) and isotropic temperature (T_i) of the corresponding monomers and polymers all decreased. However, with increasing the rigidity of the mesogenic core, T_m and T_i of the corresponding monomers and polymers all increased. TGA showed that all the polymers obtained in this study had excellent thermal stability.     

Bowlic and Polar Liquid Crystal Polymers

Bowlic liquid crystals are made up of polar molecules. Both main-chain and side-chain bowlic polymers are possible. Exactly solvable discrete models describing the phases and conformations of these bowlic and other polar liquid crystal polymers are presented. For the ideal one-dimensional case the model is equivalent to the 1D Ising model. Susceptibility and other properties are calculated. Wave propagation and solitons in these polar polymers are discussed. Possible highly conducting and high T_c superconducting liquid crystal polymers are proposed.     

Transport and Electrochemical Properties of Bi2Sr2CaCu2O8 Superconductors

Abstract

Electrical conductivity and thermoelectric power measurements (77–300K) of both the pure and electrochemically doped with lithium Bi₂Sr₂CaCu₂O₈ system, are presented. Clear correlation between transport and electrochemical properties of Li_xBi₂Sr₂CaCu₂O₈ was shown.     

Fabrication of thermo-responsive polymer nanocomposites for smart window applications

Abstract

Thermo-responsive polymers have attracted much attention in recent years because they can provide a variety of applications for smart devices, but the lack of sufficient mechanical properties and late response rate of the polymers limit their applications. In the current work, we fabricated polymer nanocomposites made from poly(vinyl methyl ether) and nanofillers with photothermal conversion property such as graphene oxide, antimony tin oxide nanoparticles, and silver nanoplates. The prepared nanocomposites showed rapidly reversible and reliable transparent-opaque transitions during the repeated heating and cooling processes, suggesting that they can be applied to smart window applications.     

Interpretation of Anomalous Absorption Spectra. A Theoretical Study of the Geometric,Electronic and Optical Properties of Poly[3-(4-Octylphenyl)-Thiophene]

Abstract

The geometric, electronic, and optical properties of poly-[3-(4-octylphenyl)-thiophene] are studied. The effect of the side groups as well as doping is analyzed. Band structures, oscillator strengths and optical absorption spectra are calculated. Absorption spectra reported for the doped polymer show up to four peaks below the band-gap energy.     

Resonance Raman Scattering of Br2 Doped Single-Walled Carbon Nanotube Bundles

Abstract

We have measured Raman spectra of bromine doped single-walled carbon nanotubes (SWNTs) using various laser lines to clarify the electronic states of the doped SWNT. In the case of evacuated sample after full doping, two breathing mode peaks were observed simultaneously by visible laser excitations. We assigned the higher frequency peak to the doped SWNT bundles, and the other peak to the undoped portions in the sample. Intensity ratio between them decreased with decreasing excitation energy, and in the infrared region, the breathing mode band of the doped bundle was not observed. These results can be explained by a simple rigid band model.     

Effects of the Anthraquinone Dye on the Electro-Optical Properties of Dye Guest-Host Polymer Dispersed Ferroelectric Liquid Crystal

Abstract

The effects of the anthraquinone dye on the electro-optical characteristics of DGHPDFLC have been investigated. The results show that PDFLC doped with dichroic dye was found to have no influence on phase separation. When dye concentration is over M483-1.0%, it causes the response time of DGHPDFLC to become slower, the frequency becomes dependent, the rotational viscosity increases, and the tilt angle becomes lower, but, on the whole, electro-optical properties are still very practical.     

Investigation of the effect of aluminum doped zinc oxide (ZnO:Al) thin films by spray pyrolysis

ABSTRACT

In this study, aluminum doped zinc oxide thin films were deposited on ordinary glass substrates at the temperature of 425°C by spray pyrolysis technique for various doping concentrations of aluminum ranging from 1 to 5 at.%. The effect of dopant concentration on structural, morphological and optical properties of ZnO:Al thin films was studied. Optical band gap of the films increased with doping percentage and started to decrease from 2 at.% of dopant. The average transmittance for 2at.% ZnO:Al film is significantly increased over 90% in the visible region at 450 nm which is crucial for optoelectronic applications.     

Electrochemical Study Of Substituted Polyparaphenylene Derivatives In Aqueous And Organic Medium

In recent years, organic conducting polymers have made concrete inroads in the field of battery materials. In the present communication we report, the synthesis and oxidation potentials of poly-p-phenylene (PPP) , polymethylphenylene (PPPmethyl), polypropylphenylene (PPPpropyl), polysulphophenylene (PPPS03H), polychlorophenylene (PPPCl), polynitrophenylene (PPPN02) and polyaminophenylene (PPPNHz). A mixture of polyvinylidene fluoride (PVF) and acetylenic carbon was used as conducting adhesive to study electrochemical properties of PPP and derivatives in acetonitrile containing 0.2 M LiCl0₄ and aqueous sulphuric acid media. We discuss the effects of the substituent groups on PPP and possibilities of its use as a battery material in the light of EPR, conductivity and electrochemical results.     

Synthetically tuned structural variations in coordination polymers based on dicyanamide toward diverse physical properties

Three new two-dimensional coordination polymers (CPs), {Ni[N(CN)₂]₂(H₂O)₂·2DMAC}_n for 1, {Ni[N(CN)₂]₂(DMAC)₂}_n for 2, and {Co[N(CN)₂]₂(DMSO)₂}_n for 3, have been synthesized with different synthetic methods. The crystallographic analysis indicates that CPs 1 and 3 crystallize in the monoclinic system with space group of P2₁/c, while CP 2 crystallizes in the orthorhombic system with space group of Pnma. CPs 1 and 3 exhibit the antiferromagnetic properties, while CP 2 shows the weak ferromagnetic property. The solid-state luminescence properties of CPs 1–3 have also been investigated. Compared with the dicyanamide, 1 and 2 show the blue shift with emission maximum around 310?nm, while CP 3 shows the band at 335?nm.