Electrochemical Synthesis of Polythiophene in an Ionic Liquid

Polythiophene (PTh) was prepared by the direct electrochemical synthesis in an ionic liquid ([BMIM]PF6) containing 0.1 mol/L thiophene by cyclic voltammetry, constant potential and constant current techniques. It is found that smooth and bluegreen PTh films can be obtained at a potential of ca. +1.75 V ( vs. Ag/AgCl ) or a current of ca. 1.5 mA cm-2 in the ionic liquid.

DEFORMATION MEASUREMENT OF CON-DUCTING POLYTHIOPHENE THIN FILMS BY AN ELECTRONIC SPECKLE PATTERN INTERFEROMETRIC METHOD

The deformation measurement of electrosynthesized polythiophene(Pth) thin films is difficult because of the small thickness and highflexibility of the specimen. An electronic speckle patterninterferom- etry (ESPI) method is used to measure the deformation ofPth films of thicknesses in the range of 4-65 μm . Theirstress-strain curves are obtained. It is found that the mechanicalproperties of Pth films are sensitive to the specimen thickness. Thetensile strength increases with decreasing thickness of thin filmfrom 10 μm. The influence of the electrochemical synthesisconditions on the mechanical properties of Pth films is also dis-Cussed.

Preparation of polythiophene/WO_3 organic-inorganic hybrids and their gas sensing properties for NO_2 detection at low temperature

Polythiophene/WO3（PTP/WO3）organic-inorganic hybrids were synthesized by an in situ chemical oxidative polymerization method,and char- acterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM）and thermo-gravimetric analysis（TGA）.The Polythiophene/ WO3 hybrids have higher thermal stability than pure polythiophene,which is beneficial to potential application as chemical sensors.Gas sensing measurements demonstrate that the gas sensor based on the Polythiophene/WO3 hybrids has high response and good selectivity for de- tecting NO2 of ppm level at low temperature.Both the operating temperature and PTP contents have an influence on the response of PTP/WO3 hybrids to NO2.The 10 wt%PTP/WO3 hybrid showed the highest response at low operating temperature of 70-C.It is expected that the PTP/WO3 hybrids can be potentially used as gas sensor material for detecting the low concentration of NO2 at low temperature.

LOW POTENTIAL ELECTROPOLYMERIZATION OF ANISOTROPIC CONDUCTIVE POLYTHIOPHENE FILMS AND FABRICATION OF ELECTRICAL DEVICES

The Complexation of thiophene with a Lewis acid with moderate acidity as a solvent, such as BF3-ethyl ether (BFEE) remarkedly lowered the electrochemical polymerization potential. The positively charged metal surface of electrode in the process of electrochemical deposition enhanced the coordination interaction between pi-electrons of thiophene unit and the metal, which makes thiophene rings lie parallel to the surface of electrode, resulting in a highly ordered polymeric structure. Because of the large intra-chain transfer integrals, the transport of charge is believed to be principally along the conjugated chains, which is much greater than the inter-chain hopping. The specific electrical resistance across the polythiophene film thickness is more than 10(4) times than that along the surface plane of the film. In this paper we review the recent development of polymerization technique by low potential electrochemical method performed in our lab and several electrical devices in which the compact polythiophene films, such as anionic and cationic sieves, and laminate film junction of undoped polythiophene derivatives were used.

Charge and spin-dependent thermal efficiency of polythiophene molecular junction in presence of dephasing

The charge and spin-dependent thermoelectric properties of different lengths of polythiophene in a molecular junction are investigated using the B ¨uttiker probe method within Green function formalism in linear response regime. The coupling of the molecular chain to three-dimensional ferromagnetic electrodes is described by a tight-binding model for both parallel and antiparallel spin configurations. The decrease of height of transmission probability peaks and thermoelectric coefficients are observed in the presence of the B ¨uttiker probes. The reduction is more intensive in the strong dephased chains.Results show that the spin magnetothermopower is bigger than the charge magnetothermopower due to the larger difference between the spin thermopowers with respect to the charge ones. In addition, we observed that the kind of carriers participating in the thermoelectric transport depends on the number of the thiophene rings.

STRUCTURAL ANALYSIS AND ENVIRONMENTAL STABILITY OF POLYFLUORINATED GROUP SUBSTITUTED POLYTHIOPHENES

Electrochemical polymerization of 3-fluoroalkoxy and 3-fluoroether thiophenes gives polymers with relatively high molecular weights and good processibility. Investigation of these polymers by means of GPC indicates that an increase in the number of fluorine atoms in the fluorinated group results in a decrease in degree of polymerization of the polymers in the same polythiophene series. As shown by NMR and FTIR, the polyfluorinated group substituted polythiophenes have regular 2, 5-coupling in their main chains. The SEM micrographs of the polymer films exhibit that polymer (1)-poly [3-2, 2, 3, 3-tetrafluoro-propoxy) thiophene] possesses more regular structure than the other polymers do. Substitution of polythiophenes by fluorinated groups leads to the polymers with high electric, electrochemical and thermal stability.

Synthesis and Characterization of Polythiophenes Bearing Diphenyl Groups in the Conjugated Chain

4,4＇-dibromo-2-nitro-biphenyl and 4,4＇-dibromo-2,3＇-dinitro-biphenyl have been synthesized via nitration reaction with 4,4＇-dibromobiphenyl as the raw material. Three novel thiophene derivatives, 4, 4＇-di（4-hexyl-thiophen-2-yl）biphenyl, 4,4＇-di（4-hexyl-thiophen-2-yl）-2- nitro-biphenyl and 4,4＇-di（4- hexyl-thiophen-2-yl）-2,3＇-dinitrobiphenyl were synthesized through Stille coupling reaction, followed by polymerization in the presence of FeC13, respectively. UV-vis absorption spectra, fluorescence spectra, photoluminescence spectra and electrochemical properties of the polymers were investigated. And the band-gap （Eg）, HOMO orbital energy （EHCMO）, and LUMO orbital energy （EUJMO） of the polymers were calculated. Among the polymers, polymer PBTN and PBTD show lower band-gap （2.67 and 2.63 eV）, lower HOMO energy level （-5.38 and -5.4 eV） and broader wavelength （432 and 438 nm） than that of polymer PBTB （2.69 eV, -5.36 eV and 424 nm） with incorporation of one nitro group or two nitro groups in the main chain, respectively.

In-situ Microscopic FT-IR Spectroelectrochemical Investigation of Polythiophene Film Modified Electrode

A polythiophene film was electrochemically deposited on a Pt micro plate electrode and investigated by cyclic voltammetry and in situ reflection microscopic FTIR spectroscopy. The FTIR analysis showed that the electropolymerization of thiophene on the Pt surface was affected by the surface adsorption processes of thiophene molecules. Two adsorption modes were identified. Two structure models of the polythiophene chain were observed simultaneously. It was proposed that the good conductibility of the polythiophene film was originated from a co vibratory equilibrium of the link part of model Ⅰ and model Ⅱ.

Polythiophene encapsulated inside(13, 0) CNT: A nano-hybrid system

We present a first-principles calculation on the electronic and optical properties of a hybrid nanotube system consisting of a （13, 0） single-walled carbon nanotube encapsulated by polythiophene. This hybrid-system represents a complete new type of matter and is known as the peapod system. We analyze bow the polythiophene changes the electronic and optical properties of the nanotube. In particular, we examine new features in the dielectric function due to the transitions between the states of the polymer and the nanotube. The electronic structure of the combined system appears to be a simple superposition of the individual constituents. The density functional theory calculations demonstrate van der Waals interaction as the bonding mechanism between the tube and the encapsulated molecule.

ELECTRONIC EFFECTS OF POLYFLUORINATED SUBSTITUENTS ON THE POLYMERIZATION AND THE PROPERTIES OF POLYTHIOPHENES

Three series of polythiophenes containing fluoroalkoxy and fluoroether substituents were prepared by electrochemical polymerization. The effect of substituents with fluoroalkoxy or ether functional groups on the electrochemical polymerization of thiophene monomers and properties of the obtained polymers were analyzed. The introduction of a fluoroether functional group at the 3-position of the thiophene ring leads to an increase of the oxidation potential of the monomer and to a decrease of the conductivity of the resulting polymers, even with the use of a CH2 group as spacer. Conversely, the presence of an oxygen atom directly at the 3-position of the thiophene ring, which offsets the negative withdrawing effect of fluoroalkyl groups, facilitates the synthesis of highly conducting polythiophenes.

Dynamical study on charge injection and transport in a metal/polythiophene/metal structure

The dynamical process of charge injection from metal electrode to a nondegenerate polymer in a metal/polythiophene （PT）/metal structure has been investigated by using a nonadiabatic dynamic approach. It is found that the injected charges form wave packets due to the strong electron-lattice interaction in PT. We demonstrate that the dynamical formation of the wave packet sensitively depends on the strength of applied voltage, the electric field, and the contact between PT and electrode. At a strength of the electric field more than 3.0 × 10^4 V/cm, the carriers can be ejected from the PT into the right electrode. At an electric field more than 3.0 × 10^5 V/cm, the wave packet cannot form while it moves rapidly to the right PT/metal interface. It is shown that the ejected quantity of charge is noninteger.

Development of Conducting Polythiophene

Polythiophene and its derivatives are getting more andmore attention as a new kind of conducting polymers.Their conductivity,application,possible processingmethods and development are discussed in this article.

Meyer-Neldel Rule in Plasma Polythiophene Thin Films

In polymers, the electronic activation energy depends on the fragmentation, crosslinking, dopants, moisture and in general on the structure-environment interaction. This has a special importance in plasma polymers because fragmentation and crosslinking are usually higher than in other polymers. In this work, DC electrical conductivity of polythiophene thin films prepared by plasma (pPTh) was studied using the Meyer-Neldel (MN) rule to calculate the characteristic MN energy and temperature as a function of moisture and metallic dopants. The experimental data for pPTh synthesized in different conditions indicated that EM = 32 meV and TM = 373 K, suggesting a thermally activated conduction mechanism;however, in polymer-metal matrices with metal concentration higher than the percolation threshold, the conduction mechanism is different causing that the MN rule was only partially fulfilled. The congruence of the experimental data with the multiexcitation entropy model is discussed.

Synthesis of Soluble Polythiophene Partially Containing 3,4-Ethylenedioxythiophene and 3-Hexylthiophene by Polycondensation

A novel poly(quinquethiophene) partially containing 3,4-ethylenedioxythiophene (EDOT) and 3-hexylthiophene, poly(3,3 ''''-dihexyl-3',4',3''',4'''-diethylenedioxy-2,2':5',2'':5'',2''':5''',2''''-quinquethiophene), was synthesized by three types of polycondensations. Among them, direct C-H coupling reaction gave the polymer with the highest molecular weight. The resulting polymer was soluble in common organic solvents. Absorption and fluorescence spectra of the polymer showed a remarkable red-shift compared with the corresponding monomer due to the expansion of effective π-conjugation length.

Metallic Interaction in Polythiophene-Ti Plasma Composites

This work presents a study about the structure and morphology of thin plasma composite films of polythiophene (PTh) with metallic particles of Ti (PTh-Ti). The objective was to study the water affinity and electric conductivity in PTh with the addition of metallic phases. The hydrophilicity was studied with the contact angles formed between water and surfaces, and the electric conductivity was calculated with the resistance measured in a two-probe device. The structure and morphology of the composites were studied with X-ray diffraction and scanning electron microscopy. The results indicated that PTh-Ti formed thin films of hybrid composites with oxidized Ti and Fe additional particles released from the electrodes used in the syntheses. The metallic fraction resulted in 2 diffraction angles at 31.6° and 66.1° product of the complex interaction among Ti, resembling orthorhombic TiO2 structures, and PTh. The metallic particles and iodine, added as a dopant to the composites to increase conductivity, reduced the hydrophilicity with water in a competition between roughness and chemical composition. In these conditions, the contact angles resulted between 46° and 75°. The electric conductivity was about 10-6 S/m increasing one order of magnitude with the metallic fraction. However, the high resistance of the polymeric fraction apparently dominates the transference of charges.

Polythiophene solar cells processed from non-halogenated solvent with 15.68%efficiency

Polythiophenes(PTs)are prospective polymer donors for large-scale manufacturing and industrialization owing to their simple structures and low synthetic cost.However,the fabrication of PT solar cells depends on highly toxic chlorinated solvents,and less research has been done on the use of more environmentally friendly non-halogenated solvents.Herein,highly efficient PT solar cells based on top-performance polythiophene,P5TCN-F25,processed from a non-halogenated solvent are reported by delicate aggregation control.A power conversion efficiency of up to 15.68%was achieved by depositing the active layer from a hot o-xylene solution,which is the record efficiency of non-halogenated processed PT solar cells up to date.The appropriate solution temperature is beneficial to the formation of ordered polymer stacking and desirable phase separation size,which thereby contributes to enhanced charge transfer efficiency,more balanced hole/electron mobility,and reduced trap-assisted recombination.These results provide valuable implications for improving the efficiency of PT solar cells via environmentallyfriendly processing.

A minimized fluorescent chemosensor array utilizing carboxylate-attached polythiophenes on a chip for metal ions detection

Chemosensor arrays have a great potential for on-site applications in real-world scenarios.However,to fabricate on chemosensor array a number of chemosensors are required to obtain various optical patterns for multianalyte detection.Herein,we propose a minimized chemosensor array composed of only two types of carboxylate-functionalized polythiophene derivatives for the detection of eight types of metal ions.Upon recognition of the metal ions,the polythiophenes exhibited changes in their fluorescence intensity and various spectral shifts.Although both chemosensors have the same polymer backbone and recognition moiety,only the difference in the number of methylene groups contributed to the difference in the fluorescence response patterns.Consequently,the metal ions in aqueous media were successfully discriminated qualitatively and quantitatively by the chemosensor microarray on the glass chip.This study offers an approach for achieving a minimized chemosensor array just by changing the alkyl chain lengths without the necessity for many receptors and reporters.

Calculation aided miscibility manipulation enables highly efficient polythiophene:nonfullerene photovoltaic cells

Polythiophenes,with merits of low cost and high scalability of synthesis,have received growing interest in organic solar cells.To date,the best-performing polythiophene:nonfullerene solar cells exhibit typical power conversion efficiencies (PCEs) of 10%–12%,which is much lower than those employing PM6-and D18-type polymers.This inferior performance is mostly limited by the improper miscibility between polythiophene and acceptors.Efforts on engineering the molecular structure to systematically tune the miscibility are required.With the aid of group contribution calculations,the miscibility of polythiophene:nonfullerene blend system was finely tuned by varying the ratios of siloxane-terminated chains and alkyl chains in ester-substituted polythiophenes through random copolymerization.Based on a series of the polythiophene and nonfullerene acceptors,the detailed analysis of blend miscibility and performance reveals a surprising anticorrelation between the Flory-Huggins interaction parameter (χ_(aa)) and the optimal time of solvent vapor annealing for device performance across these systems.Primarily due to the slightly higher χ_(aa),the blend of PDCBT-Cl-Si5 and ITIC-Th1 results in a record-high PCE of 12.85%in polythiophene:nonfullerene solar cells.The results not only provide a calculation-guided approach for molecular design but also prove that precise control of the miscibility is an effective way to design high-performance polythiophene:nonfullerene blends and beyond.

Visual sensing of picric acid in 100% aqueous media based on supramolecular polythiophene assemblies with colorimetric and fluorescent dual response

A colorimetric and fluorometric dual probe based on a water-soluble polythiophene derivative(PMTPBA)was designed and synthesized.It can be applied to determination of picric acid(PA) in 100% aqueous solution.The approach relies on the formation of supramolecular polythiophene assemblies in the presence of PA through electrostatic,charge transfer and π-π stacking interactions.This probe could be utilized for the rapid and visual detection of PA both in aqueous solution and solid support with high specificity and sensitivity.The detection limit of this sensor is as low as 5.0 × 10^-8 mol/L.

Microporous polythiophene(MPT)-guest complex derived magnetic metal sulfides/carbon nanocomposites for broadband electromagnetic wave absorption

Electrical and magnetic properties are two crucial factors for the designing of broadband electromagnetic wave absorption(EWA)materials.In this work,we synthesized various magnetic metal sulfides/carbon(M_(x)S_(y)/C)nanocomposites from the precursor complex of metal in microporous polythiophene(MPT),and systematically investigated their EWA properties and mechanism.The characterization results indicate that M_(x)S_(y) were determined to be Fe_(7)S_(8)/C,Co_(9)S_(8)/C and Ni_(4)S_(3)/C,respectively.It is observed that M_(x)S_(y)/C nanocomposites exhibit remarkable EWA performances,where the maximal absorption gets to-51.3 dB,and efficient absorption can be realized in 10.32-18 GHz(7.68 GHz),which is superior to most reported magnetic carbonaceous EWA composites.Beside,the efficient absorption can be tuned to cover Ku band X band,demonstrating their great potential in practical applications.Improved conductance loss,obvious polarization relaxation,and apparent eddy current loss are deemed to make the predominant contributions to the high-performance EWA.This research opens up the exploration of novel nanocomposite coupling dielectric loss and magnetic loss using MPT-metal complex precursor for EWA applications.