Electrical and optical properties of a novel nonconjugated conductive polymer,poly(β‐pinene)

Electrical conductivity in a novel nonconjugated conductive polymer, poly(β‐pinene), has been measured as a function of molar concentration of iodine. The conductivity increases about 10 orders of magnitude to a maximum value ?8 × 10^?3 S/cm. The molar concentration of iodine, corresponding to saturation, is ?0.85. The optical absorption measurements after light doping have shown two peaks: one at 4.0 eV and the other at 3.1 eV. The first peak is due to the radical cation, and the second due to the charge‐transfer between the double bond and the dopant. As observed in other nonconjugated conductive polymers, the second peak becomes broader and undergoes a red shift, upon higher doping. The FTIR spectroscopic studies have shown that the C?C stretching vibration at 1610 cm^?1 and the ?C? H bending vibration band at 728 cm^?1 decrease upon doping, because of decrease of double bonds. Photoluminescence studies of poly(β‐pinene) show a maximum value at 360 nm for excitation at 280 nm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3695–3698, 2005     

Photovoltaic Cells Involving the Nonconjugated Conductive Polymer Iodine-Doped Styrene-Butadiene-Rubber (SBR)

Novel photovoltaic cells involving a nonconjugated conductive polymer have been fabricated using titanium dioxide/doped styrene-butadiene-rubber/carbon on ITO coated PET substrates. Photocurrents and photo-voltages for different intensities of light (emission at 300–700 nm) have been measured. These cells have shown significantly higher photocurrents and photo-voltages compared to previous reports. A photocurrent density of about 0.25 mA/cm² and a photo-voltage of 0.74 V have been measured for a light intensity of ～4 mW/cm².     

Electrical conduction in a nonconjugated polymer doped with SnCl4 and SbCl5

The electrical and optical properties of 1,4-cis-polyisoprene before and after doping with SnCl₄ and SbCl₅ were investigated. The material becomes reddish brown and black upon doping with SnCl₄ and SbCl₅, respectively, and the conductivity increases by about 11 orders of magnitude. The optical absorption, infrared spectra, elemental analyses, and the studies of reversibility upon compensation indicate that radical cation formation is the most likely mechanism for electrical conduction in these complexes. The results are consistent with previously published articles involving iodine doping. © 1994 © John Wiley & Sons, Inc.     

Photo-induced Charge-transfer and Photovoltaic Effect in a Composite Involving a Nonconjugated Conductive Polymer and C60

Photo-induced charge-transfer and resulting photovoltaic effect in a composite involving a nonconjugated conductive polymer, poly(β -pinene) and C₆₀ is reported. The photovoltaic cell was fabricated using indium-tin-oxide coated glass as one electrode and aluminum as the other, with poly(β -pinene)-C₆₀ composite film sandwiched in-between. A Nitrogen laser (325 nm) and an illuminant white-light-source (300–700 nm) were used and the photo-voltage produced was found to have a linear dependency on light intensity. The photoluminescence of poly(β -pinene) (at 360 nm) was quenched when C₆₀ was added to form the composite. Therefore, the photovoltaic effect is a result of excited-state electron-transfer from poly(β -pinene) to C₆₀.     

Photovoltaic properties of the polymer solar cells comprising crosslinked maleimide polymers and fullerene‐derivative PCBM

A series of crosslinkable maleimide conjugated polymers with different vinyl group contents as side‐chain crosslinking sites have been synthesized by the Suzuki coupling reaction. Polymer solar cells (PSCs) were fabricated based on an interpenetrating network of the crosslinkable maleimide polymers as the electron donor, and a fullerene derivative, (6,6)‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM), as the electron acceptor. The crosslinkable maleimide polymers underwent crosslinking reaction at the side‐chain vinyl groups upon the thermal treatment with or without the addition of initiator, azobisisobutyronitrile (AIBN). Better photovoltaic (PV) performances were obtained for the PSCs based on the polymer crosslinking without using initiator, whereas poorer PV performances were observed for the PSCs based on the polymer crosslinking with the AIBN initiator. In addition, higher operational stability was observed for the crosslinked polymer based solar cell as compared to the solar cell based on the un‐crosslinked polymer. The photo‐physical and PV properties of the cross‐linked maleimide polymers/PCBM based PSCs are discussed in detail as the morphology and crosslinking density of the polymers are taken into account. Copyright © 2010 John Wiley & Sons, Ltd.     

Photovoltaic devices from CdSe nanocrystals and conjugated polymer composites

The preparation of CdSe nanospheres (ns-CdSe) and their application as electron acceptor in conjugated polymer photovoltaic devices are reported. ns-CdSe with diameters of 5 nm were prepared through an organometallic method. The transmission electron microscopy (TEM), ultraviolet-visible (UV-Vis) absorption and photoluminescence (PL) spectra indicate that the CdSe nanocrystals (NCs) are monodispersed nanospheres with the first exciton absorption peak at around 625 nm and the emission peak at around 652 nm. The PL spectra of the ns-CdSe/polymer composite films show that the PL of the conjugated polymers is effectively quenched upon the addition of ns-CdSe. Photovoltaic devices were fabricated from the composites of ns-CdSe and poly[2-methoxy-5-(2′-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) or poly(3-hexylthiophene) (P3HT). Under AM1.5 illumination (100 mW/cm²), the short circuit current (I _SC), open circuit voltage (V _OC), fill factor (FF) and energy conversion efficiency (η) reached 1.56 mA/cm², 0.75 V, 34.5% and 0.40%, respectively for device from the ns-CdSe/MEH-PPV (15: 1 by weight) and 1.93 mA/cm², 0.65 V, 38.4% and 0.48%, respectively for device from the ns-CdSe/P3HT (10: 1 by weight). __________ Translated from Chemical Journal of Chinese Universities, 2007, 28(3): 596–599 [译自: 高等学校化学学报]     

高分子导热复合材料结构设计及性能研究进展

近年来,电子设备的需求逐渐向集成化、微型化发展,随之带来了愈发严重的发热问题已经成为了阻碍电子设备发展的重要因素之一。作为电子设备重要组成材料之一的高分子材料对优良导热性能的要求也越来越高,导热高分子复合材料的研究已经成为当前功能复合材料的重要发展方向。本文综述了高分子导热复合材料的发展趋势,介绍了当前选用填料法来制备单一填料、混杂填料高分子导热复合材料以及双逾渗结构、隔离结构等复杂多相结构的高分子导热复合材料的研究进展。重点介绍了通过多种导热填料的组合利用来制备高性能导热高分子复合材料。最后,对填料法高导热高分子复合材料的发展方向做出了简要展望。     

Thermoresponsive conductive polymer composite thin film and fiber mat: Crosslinked PEDOT:PSS and P(NIPAAm‐co‐NMA) composite

The thermoresponsive conductive composite (TCC) thin films and fiber mats, whose electrical property changed with temperature, were fabricated successfully. The thermocrosslinkable and thermoresponsive copolymer, poly(N‐isopropyl acrylamide‐co‐N‐methylolacrylamide) (PNN), was synthesized. The TCC thin film and fiber mat were fabricated by spin coating and electrospinning process of PEDOT:PSS/PNN solutions, respectively. After thermocrosslinking and doping by DMSO, the composite thin films and fiber mats were obtained. Fibrous structures of TCC fiber mats were observed by SEM. The surface resistance and conductivity of composites were measured. The thermoresponsivity and swelling ratio of TCCs were also studied. The thermoresponsive conductive property was analyzed by measuring the surface resistance of TCCs in water bath under various temperatures from 20 to 50 °C. With the increase of temperature, the TCCs shrank to be dense structure and showed lower surface resistance. The TCC fibers mat exhibited greater sensitivity to temperature than thin film owing to its fibrous structure. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1078–1087     

An approach to one‐dimensional conductive polymer composites

A substantial approach to one‐dimensional (1D) electrically conductive composites was proposed which was based on the thermodynamic analysis of electric‐field‐induced particle alignment in a nonpolar thermoplastic polymer matrix. The process condition window was based on the real‐time exploration of dynamic percolation under different electric fields with carbon black (CB)‐filled polyethylene as a model. The CB content was the main factor of the process condition. Its upper limit was set as the critical percolation concentration at the thermodynamic equilibrium state without an electric field to eliminate the possibility of conductive network formation perpendicular to the electric‐field direction, whereas its lower limit the critical percolation concentration at the thermodynamic equilibrium state under a critical electric field (E*). A composite with CB content in this window, isothermally treated in an electric field not less than E*, showed conductivity in the electric‐field direction about 10⁵ times larger than that in the perpendicular direction. A 1D cluster structure in the direction of the electric filed was confirmed with scanning electron microscopy morphology observations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 184–189, 2005     

Properties of conductive polymer hydrogels and their application in sensors

Conductive polymer hydrogels (CPHs), which combine the unique advantages of hydrogels and organic conductors, have received wide attention due to their adjustable mechanical properties, biocompatibility, self‐healing, hydrophilicity, and ease of preparation. With doping engineering and incorporation with other functional nanomaterials, CPHs have exhibited excellent physical/chemical properties. CPHs have been widely used in various electronic devices, especially in the field of sensors due to its sensitivity to external stimuli. This review summarizes recent progress in CPHs from the aspect of the CPHs' properties and their application in advanced sensor technology. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1606–1621     

Influence of graphene reinforcement in conductive polymer: Synthesis and characterization

Lightweight conductive polymers are considered for lightning strike mitigation in composites by synthesizing intrinsically conductive polymers (ICPs) and by the inclusion of conductive fillers in insulating matrices. Conductive films based on polyaniline (PANI) and graphene have been developed to improve through‐thickness conductivity of polymer composites. The result shows that the conductivity of PANI enhanced by blending polyvinylpyrrolidone (PVP) and PANI in 3:1 ratio. Conductive composite thin films are prepared by dispersing graphene in PANI. The conductivity of composite films was found to increase by 40× at 20 wt% of graphene inclusion compared with PVP and PANI blend. Fourier‐transform‐infrared (FTIR) spectra confirmed in situ polymerization of the polymer blend. The inclusion of graphene also exhibits an increase in Tg by 21°C. Graphene additions also showed an increase in thermal stability by approximately 148°C in the composite films. The mechanical result obtained from DMA shows that inclusion of graphene increases the tensile strength by 48% at 20 wt% of graphene reinforcement. A thin, highly conductive surface that is compatible with a composite resin system can enhance the surface conductivity of composites, improving its lightning strike mitigation capabilities.     

聚合物太阳电池光伏材料

聚合物太阳电池由共轭聚合物给体和可溶性富勒烯衍生物受体的共混膜夹在ITO透光电极和金属电极之间所组成,具有结构简单、成本低、重量轻和可制成柔性器件等突出优点,近年来受到广泛关注。聚合物太阳电池中的给体和受体光伏材料是决定器件性能的关键。本文综述了共轭聚合物给体和富勒烯受体光伏材料的最新研究进展,对共轭聚合物受体材料和给体-受体双缆型共轭聚合物光伏材料的研究进展也进行了简要介绍。在共轭聚合物给体材料中对聚噻吩衍生物以及含有苯并噻二唑的窄带隙D-A共聚物进行了重点介绍。     

Enzymatic‐catalyzed polymerization of water‐soluble electrically conductive polymer PEDOT:PSS

Water‐soluble electrically conductive polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) was synthesized by the enzymatic‐catalyzed method using 3,4‐ethylenedioxythiophene (EDOT) as monomer, poly(styrenesulfonate) (PSS) as water‐soluble polyelectrolyte, horseradish peroxidase enzyme as catalyst, and hydrogen peroxide (H₂O₂) as oxidant. Fourier transform infrared spectra and UV–vis absorption spectra confirm the successful enzymatic‐catalyzed polymerization of PEDOT. Dynamic light scattering data confirm the formation of a stable PEDOT:PSS aqueous dispersion. The thermo gravimetric data show that the obtained PEDOT is stable over a fairly high range of temperatures. The atomic force microscopy height images show that the PEDOT:PSS aqueous dispersion can form excellent homogeneous and smooth films on various substrates by conventional solution processing techniques, which renders this PEDOT:PSS aqueous dispersion a very promising candidate for various application in electronic devices. This enzymatic polymerization is a new approach for the synthesis of optical and electrical active PEDOT polymer, which benefits simple setting, high yields, and environmental friendly route. Copyright © 2014 John Wiley & Sons, Ltd.     

A 3D printable self-healing composite conductive polymer for sensitive temperature detection

Recent development of self-healing material has attracted tremendous attention,owing to its biomimetic ability to restore structure and functionality when encountering damages.Here,we develop a threedimensional(3D)printable self-healing composite conductive polymer by mixing hydrogen-bond-based supramolecular polymer with low-cost carbon black.It has a room-temperature self-healing capability in both conductivity and mechanical property,while its shear-thinning behavior enables fabrication of a self-healable circuit by 3D printing technology.As an application,the circuit shows an excellent temperature-dependent behavior of the resistance,indicating its great potential fo r practical application in the artificial intelligence field.     

基底温度对刮涂制备的P3HT:PCBM薄膜形貌和光伏电池性能的影响

研究了刮涂制备P3HT:PCBM(P3HT:聚3-己基噻吩,PCBM:[6,6]-苯基-C61-丁酸甲酯)活性层的过程中,基底温度对P3HT:PCBM活性层薄膜性质和电池性能的影响.结果表明,提高基底温度在缩短薄膜干燥时间的同时,抑制了PCBM相的大尺度聚集,并改善了P3HT:PCBM薄膜中P3HT在(100)方向上的结晶程度,但降低了π-π共轭方向上的有序度.制备的光伏电池经过进一步退火处理后可形成良好的互穿网络结构,能量转换效率可达3.93％.     

Synthesis and electronic properties of poly (E,E)-[6.2]-(2,5) thiophenophane-1,5-diene)

Cationic cyclopolymerization of (E, E)-[6.2]-(2,5) thiophenophane-1,5-diene ( 2 ) gave polymer 3 which has bridged thiophene rings pendant to the polymer backbone. The structural, thermal, and electronic properties of polymer 3 were compared to those of its benzene analogue ( 1 ) and its nonbridged analogue poly (2-vinylthiophene) ( 5 ). The onsets of thermal degradation for polymers 3 and 5 under helium were 425 and 382°C, respectively. Polymer 3 exhibited conductivity in the 10^?3?10^?4 S/cm range when exposed to iodine vapor, four orders of magnitude higher than for 5 treated in the same manner. Apparent energies of activation for conductivity in iodine saturated polymers 3 (0.57 eV) and 5 (0.61 eV) were calculated from conductivity temperature dependence measurements. Conductivity parameters for iodine saturated 3 show both a higher level of conductivity and weaker temperature dependence than for the corresponding cyclopolymer 1 which has benzene rather than thiophene moieties, suggesting that greater charge generation occurs in 3 , due to the lower oxidation potential of the thiophenophane repeat units. Differences in conductivity behavior for iodine saturated polymers 1, 3 , and 5 are discussed in terms of both charge generation and mobility. © 1994 John Wiley & Sons, Inc.     

导电聚苯胺的热分析及粘弹性能研究

本文用热分忻的方法和粘弹谱仪对聚苯胺（ＰＡＮ）的热性能和粘弹性进行了研究．结果表明ＰＡＮ的耐热性较好，本征态（非掺杂）ＰＡＮ的玻璃化转变温度为 １３４℃，转变活化能为 ２７３ＫＪ／ｍｏｌ．     

Ion conductive poly(ethylene oxide-dimethyl siloxane) copolymers

A series of poly(ethylene oxide-dimethyl siloxane) copolymers, — [SiMe₂O(CH₂CH₂O)_n]_m — (n = 2, 3, 4, 5, 6.4, 8.7, 13.3), were synthesised by the reaction of polyethylene glycol with dimethyl dimethoxy/diethoxysilane. Corresponding ion-conductive polymers were prepared by complexing these copolymers with salts (sodium tetrafluoroborate or ammonium adipate). The highest conductivity of these systems at room temperature was 3 × 10⁻⁴ S cm⁻¹ and 6 × 10⁻⁵ S cm⁻¹, respectively. The glass transition temperature of these copolymers is reported and is seen to be dependent on the length of the ether units. The effects of siloxane content, salt concentration, and temperature on the conductivity are discussed. © 1996 John Wiley & Sons, Inc.     

Molecular design of a π‐conjugated single‐chain electronically conductive polymer

This study demonstrates that single‐chain π‐conjugated systems can be made electrically conductive by modifying the molecular structures of both ends of the oligomers making up a polymer. That is, the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gaps of a fairly long polyyne‐type oligomer with appropriately modified molecular structures at both ends are found to be on the order of thermal energy by calculations using density functional theory (DFT) with B3LYP functionals. This result applies to molecular structures with characteristic bond alternations. The peculiar bond alternations are caused by competition between two effects of the bond alternations of the two mutually perpendicular π‐conjugated systems, which partially cancel each other out. It is probable that we can design one‐dimensional polymers with HOMO–LUMO gaps small enough to be conductive by combining the above‐mentioned oligomers with each other as monomer units in the polymer. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Transparent conductive films based on polymer composites containing the mixed‐valence tetrathiafulvalene nanofibers

We report the facile preparation of the conductive polymer composites containing the mixed‐valence tetrathiafulvalene (TTF) nanofibers and their applications as all‐organic transparent conductive materials. TTF can be used as a nanofiller for transforming conventional polymers to conductive materials. Self‐assemble nanofibers of the neutral and radical cation of TTF can be formed in the polymer solutions during the film deposition, and the resulting composite films with several micron thickness can serve as the conductive material with high transparency. Several kinds of conventional polymers, such as polystyrene, poly(methyl methacrylate) (PMMA), and poly(vinylpyrrolidone), can be used as a polymer matrix of the composites. The conductivities of the PMMA film containing 35 mol % of the mixed‐valence TTF and the PEDOT–PSS film showed similar values (2.8 × 10^–2 and 5.4 × 10^–1 S/cm, respectively). In contrast, the normalized transmittance of the PMMA film by 1‐μm thickness greatly increased (96%/μm) when compared with that of the PEDOT–PSS film (10%/μm). In addition, the degradation of the conductivity of the nanofibers by heating and aging was effectively suppressed in the composite samples. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6441–6450, 2009