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Complex Optical and Thermal Studies on As-Synthesized Conducting Polythiophene
摘要： A series of conducting polythiophene (PTh) samples have been synthesized using an in situ chemical oxidative polymerization technique in aqueous solution. The characterization of the as-synthesized optimized sample has been carried out by Fourier transform infrared spectroscopy, x-ray diffraction and thermogravimetric–differential thermal analysis techniques. Also, the complex optical parameters of all the as-synthesized polymeric samples have been investigated by using ultraviolet–visible spectroscopy. The as-synthesized polymeric samples exhibited absorption around 220–280 nm. The optical band gap was found to ranges from 5.06 eV to 5.24 eV. The maximum optical conductivity for the sample with a stoichiometric ratio of thiophene to FeCl3 of 70:30 wt.% was found to be 5.973 9 108 S cm?1 at 280 nm. The experimental results reveal that the thermal and optical performance of conducting PTh can be dramatically enhanced for the sample with a stoichiometric ratio of thiophene to FeCl3 of 70:30 wt.%. The improved complex optical properties of as-synthesized samples of conducting PTh validate their potential utilization in optoelectronic devices.
关键词： thermal analysis,complex optical properties,Polythiophene
更新于2025-11-19 16:56:35
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Time-dependent DFT and experimental study on visible light photocatalysis by metal oxides of Ti, V and Zn after complexing with a conjugated polymer
摘要： Density Functional Theory (DFT) and Time Dependent (TD)-DFT studies predict substantial modifications in optical properties of Transition Metal Oxides (TMOs) of Ti, V and Zn by complexing them with conjugated polymer polythiophene (PTh). The TMO nanostructures were synthesized and their complexes with polymers were fabricated using a chemical oxidative polymerization method. Coating of the TMOs with PTh and the nano-dimensional nature of the samples was confirmed by various morphological investigations such as infrared (IR), X-ray di?ractographs (XRD), High Resolution Transmission Electron Microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM) techniques. The prepared samples were found to be a visible light driven photocatalyst. The sensitization of the complexes has been explained in terms of relative ordering of frontier orbitals of PTh and the TMO, and PTh qualified as an e?cient photosensitizer for all three metal oxides on the basis of its electronic characteristics. Since the Highest Occupied Molecular Orbital (HOMO) of PTh lies well between the band gap of all three TMOs, the electron transfer from donor (PTh) to acceptor (TMO) is facilitated. The appreciable red shift in the absorption spectrum and decrease in the optical band gap calculated by Tauc’s plot confirmed substantial reduction in the band gap of the formed complex in comparison to their bare counterparts. The isodensity plots established the PTh–TMO complexes as donor acceptor complexes and intermolecular charge transfer quantified the electron transfer from PTh (donor) to the TMOs (acceptor).
关键词： conjugated polymer,TD-DFT,visible light,metal oxides,DFT,photocatalysis,polythiophene,band gap tuning
更新于2025-11-14 17:04:02
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Polythiophene–PCBM-Based All-Organic Electrochromic Device: Fast and Flexible
摘要： A fast and ?exible all-organic electrochromic device, fabricated using polythiophene and PCBM as active materials and plastic substrate, which shows very good power e?ciency as well, has been reported here. The device shows quanti?able improvement in electrochromic performance using parameters like switching speed, coloration e?ciency, color contrast, and cycle life. Spectroscopic investigations have been carried out using Raman and UV?vis to establish a bias induced redox switching based mechanism for the reported improvement in the performance. The device shows switching between magenta (OFF) and transparent states (ON) with a very small bias of ±1 V, an optical modulation of 50% and an absorbance switching contrast of 91%. An enhanced stability for a duration of longer than 2500 s and 250 cycles has been reported with an ultrafast response of few hundred milliseconds. A very high coloration e?ciency of 321 cm2/C is achieved, making the proposed device one of the best reported P3HT-based electrochromic devices.
关键词： PCBM,electrochromic,polythiophene,?exible devices,organic electronics
更新于2025-09-23 15:22:29
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Design, characterization, optical and photophysical properties of novel thiophene monomers and polymers containing pyrene moieties linked via rigid and flexible spacers
摘要： Herein, we report the synthesis of three novel thiophene monomers connected to pyrene moieties via a flexible oligo(ethylene glycol) (OEG) spacer with an oxygen α-to-pyrene (T1), a flexible OEG spacer with an oxygen β-to-pyrene (T2), and a rigid acetylene spacer (T3). These monomers were prepared in an easy manner from commercially available 3-bromo-4-methylthiophene and further characterized by NMR spectroscopy and mass spectrometry. Monomer T2 exhibited the absorption band at 344 nm and a strong 'monomer' emission band at 375 nm typical of a 1-pyrenemethyl derivative. Moreover, T1 and T3 showed red shifted absorption bands at 352 and 384 nm arising from the pyrene substituents, namely the electron-donating oxygen α-to-pyrene and the extended conjugation length, respectively. These compounds exhibited a broad 'monomer' emission band between 360–480 nm without excimers. Homopolymers (OHP1, OHP2, and OHP3) obtained from these monomers were partially soluble and their photophysical properties such as quantum yield and lifetime were characterized. Emission spectra of the oligomers OHP1 and OHP3 exhibited an emission band at ~500 nm, which is due to the conjugated polythiophene backbone and does not arise from intramolecular pyrene-pyrene interactions.
关键词： Pyrene,Polythiophene,Optical properties,Fluorescence
更新于2025-09-23 15:22:29
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Significant Enhancement of Hole Transport Ability in Conjugated Polymer/Fullerene Bulk Heterojunction Microspheres
摘要： Bulk heterojunction (BHJ) strategy requires morphology of wide area donor-acceptor interfaces with high charge carrier mobilities through the bicontinuous charge transporting layers. Here, we report formation of well-defined bulk heterojunction (BHJ) microspheres from regiorandom poly(hexylthiophene) (rra-PHT)/phenyl-C61-butyric acid methyl ester (PCBM) mixture by a vapor diffusion method. By electrochemical oxidation, the BHJ microsphere exhibits enhanced generation of PHT cation species due to increased hole-transport property in comparison with a solution-cast film derived from rra-PHT/PCBM mixture without microsphere morphology. Photoconductivity and electrochemical stability of the microsphere are comparable or even higher than a cast film of irregular aggregates of regioregular P3HT.
关键词： polythiophene,bulk heterojunction,microspheres,electrochemistry,fullerene
更新于2025-09-23 15:22:29
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Synthesis and Properties of Novel Thiophene-Based Liquid Crystalline Conducting Polymers
摘要： Side-chain liquid crystalline polythiophenes were synthesised and the effects of the mesogenic units on the structure and electronic properties of the polymers were studied. The liquid crystal properties of the polymer films were studied using polarised hot-stage optical microscopy and differential scanning calorimetry, and X-ray diffractometry was used to investigate the effect of a magnetic field on the monomers and polymers.
关键词： Polythiophene,Conducting polymers,Liquid crystals,X-ray diffraction,Magnetic field
更新于2025-09-23 15:22:29
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Modified Electrodes with Polymers Based on Aniline and Thiophene: Characterization and Possible Use as a Sensor
摘要： A systematic steel and platinum electrodes were modified via drop-coating with polymers based on aniline and thiophene or aniline and 3-alkylthiophene previously synthesized and reported by us. Having in mind the possible applications of these materials, electrochemical (cyclic voltammetry, CV, the in different electrolytic solutions), morphological and RAMAN characterization of electrode|polymer systems was accomplished, using platinum or stainless steel discs of 0.07 cm2 geometric area as electrode substrates and poly[4-(2-thiophene)aniline], PTANI, poly [4-(3-methyl-2-thiophene)-aniline], PTANIr1, and poly [4-(3-hexyl-2-thiophene)-aniline], PTANIr2 polymer coatings. A suspension of the respective polymer in tetrahydrofuran was filtered and drops of the soluble fraction of each polymer was deposited on the electrode surface, allowing the solvent to evaporate between each drop, until the whole electrode surface was coated. n- and p-doping study was accomplished by CV in a 1.0·10-3 mol L-1 NaF solution, using 0.05 mol L-1 LiClO4 as supporting electrolyte. Thus, it was revealed that only the Pt|PTANI electrode displayed p-doping process, so it may be tried for anions removal or as an analytical sensor for this kind of species. Instead, PTANIr1 and PTANIr2 could be suggested as fluorescence sensors, while the absence of p- and n-doping processes of the PTANIr2 system on steel and platinum electrodes, makes it a good candidate for metallic corrosion inhibition, since it is highly stable towards potential changes without damaging the deposited polymeric film.
关键词： polythiophene,poly[4-(2-thiophen)-aniline],poly[4-(3-hexyl-2-tiophen)-aniline],poly[4-(3-metyl-2-tiophen)-aniline],polyaniline,modified electrodes
更新于2025-09-23 15:21:01
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Structural, morphological and electrochemical properties of long alkoxy-functionalized polythiophene and TiO2 nanocomposites
摘要： High performance alkoxy-functionalized polythiophene (PM4EOT) and TiO2 nanocomposites were prepared via a facile in situ oxidative chemical polymerization of thiophene monomer. The morphology studied demonstrated that nanocomposites were of the core–shell structure with a particle size of approximately 30 nm and PM4EOT shell was of about 2–10 nm thickness. X-ray photoelectron spectroscopy (XPS) spectra proved that there was a new Ti–S interaction between the polymer and TiO2 surface. The supercapacitive behaviors of the nanocomposites investigated by cyclic voltammetry galvanostatic charge–discharge and AC impedance measurements demonstrated that the prepared PM4EOT/TiO2 nanocomposite [1:1 (weight ratio)] exhibits enhanced specific capacitance and cycling stability as compared to the two pristine components and various ratio contents. The specific capacitance of PM4EOT/TiO2 nanocomposite (1:1) was obtained up to 111 F/g at a current density of 0.5 A/g, which is much higher than that of the pure PM4EOT (45 F/g) and TiO2 (1.6 F/g). In addition, the energy density of 15.4 Wh kg?1 and the power density of 308 W kg?1 delivered by composite (1:1) capacitor were achieved at a current density of 0.5 A/g.
关键词： specific capacitance,TiO2 nanocomposites,supercapacitive behaviors,alkoxy-functionalized polythiophene,energy density
更新于2025-09-23 15:21:01
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Silsesquioxane-Polythiophene Hybrid Copolymer as an Efficient Modifier for Single-Walled Carbon Nanotubes
摘要： One silsesquioxane-polythiophene hybrid copolymer, with combined star-like structure and intramolecular heterogeneity, was synthesized and sufficiently characterized via various methods, including FTIR, NMR, and SEC measurements. According to the exploration and characterization results, it was much more efficient at modifying SWNTs than its linear analogs in aqueous solution. The hydrophobic silsesquioxane core and PEDOT chains could locally anchor to the surface of the nanotubes, while the soluble flexible copolymer chains extended into the solution and rigid conjugated chains provided some π-π stacking effect to enhance adhesive force with the conjugated structure of the carbon nanotube, imparting steric stabilization to nanotube dispersion. The noncovalent interaction with SWNTs and solubility in aqueous solution improved the electrochemical characteristics of the modified-SWNT composite and availed for the preparation of a flexible and transparent electroactive film. Accordingly, this kind of silsesquioxane-polythiophene hybrid copolymer will be forwarded to apply to the assembling of flexible optoelectronic devices.
关键词： silsesquioxane-polythiophene hybrid copolymer,single-walled carbon nanotubes,noncovalent modification,electrochemical characteristics,aqueous solution
更新于2025-09-23 15:19:57
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Comparing blends and blocks: Synthesis of partially fluorinated diblock polythiophene copolymers to investigate the thermal stability of optical and morphological properties
摘要： The microstructure of the active blend layer has been shown to be a critically important factor in the performance of organic solar devices. Block copolymers provide a potentially interesting avenue for controlling this active layer microstructure in solar cell blends. Here we explore the impact of backbone fluorination in block copolymers of poly(3-octyl-4-fluorothiophene)s and poly(3-octylthiophene) (F-P3OT-b-P3OT). Two block co-polymers with varying block lengths were prepared via sequential monomer addition under Kumada catalyst transfer polymerisation (KCTP) conditions. We compare the behavior of the block copolymer to that of the corresponding homopolymer blends. In both types of system, we find the fluorinated segments tend to dominate the UV–visible absorption and molecular vibrational spectral features, as well as the thermal behavior. In the block copolymer case, non-fluorinated segments appear to slightly frustrate the aggregation of the more fluorinated block. However, in situ temperature dependent Raman spectroscopy shows that the intramolecular order is more thermally stable in the block copolymer than in the corresponding blend, suggesting that such materials may be interesting for enhanced thermal stability of organic photovoltaic active layers based on similar systems.
关键词： fluorination,conjugated block-copolymer synthesis,microphase stabilization,polythiophene,temperature-dependent Raman spectroscopy
更新于2025-09-19 17:15:36