山梨醇掺杂对PEDOT:PSS薄膜结构与性能的影响

为改善聚乙撑二氧噻吩:聚(对苯乙烯磺酸)根阴离子(PEDOT:PSS)薄膜的光学及电学性能,采用共混-旋涂法在石英玻片上制备出山梨醇掺杂的PEDOT:PSS透明导电膜.利用X射线衍射仪(XRD),傅立叶变换拉曼光谱(FT-RM),原子力显微镜(AFM),场发射扫描电子显微镜(FE-SEM),紫外-可见吸收光谱(UV-Vis)及四点探针法对薄膜的微结构与性能进行了研究.XRD结果显示山梨醇的掺杂未改变薄膜的聚集态结构;FT-RM表明PEDOT的主要特征峰发生红移,主链结构发生苯-醌转变,分子间作用力增大,导致薄膜表面粗糙度增大,横截面出现索状条纹;薄膜透光率在600～900nm略有升高,导电性能有较大提高,最佳掺杂浓度下,薄膜电导率可达到105S/cm.     

基于导电聚苯胺的离子凝胶柔性驱动器研究

基于导电聚合物的柔性电化学驱动器具有驱动电压低，成本低和环境适应性强等特点，在柔性驱动领域具有重要的研究意义。分别以硫酸和植酸作为掺杂剂合成导电聚苯胺，借助扫描电子显微镜和X射线衍射仪等表征方法，研究了掺杂剂对聚苯胺微观结构的影响。将掺杂态的导电聚苯胺作为添加剂加入到PEDOT∶PSS驱动器电极中，获得了一种具有高拉伸和高导电性(925S/cm)的电极，并且驱动器的最大质量电容可达到1F/g,最大弯曲位移为5.6mm。结果表明：聚苯胺作为添加剂对驱动器的驱动性能有较大的提升作用，为后续的研究提供了有益的借鉴意义。     

溴掺杂对PEDOT/PSS薄膜性能的影响及机理研究

为改善聚乙撑二氧噻吩∶聚（对苯乙烯磺酸）根阴离子（PEDOT/PSS）薄膜的光学及电学性能,采用共混-旋涂法在石英玻片上制备出溴掺杂的PEDOT/PSS透明导电膜,并就其掺杂导电机理进行了探讨.结果表明：经微量溴掺杂后的PEDOT/PSS薄膜,其透光性能与导电性能均得到提高;质量分数6%溴掺杂条件下,薄膜透光率为95....     

PEDOT基对电极染料敏化太阳能电池研究进展

染料敏化太阳能电池(DSSC)是新型太阳能电池的研究热点之一,其优异的弱光发电性能被不断探索,同时透明及柔性DSSC在可穿戴设备上的应用也与日俱增。DSSC的循环依靠对电极的作用才能及时高效地完成,因此对电极材料的选择尤为关键。近几年研究者们对对电极材料的研究不断深入,其中可作为DSSC对电极材料使用的高分子导电聚合物聚3,4-乙撑二氧噻吩(PEDOT)因其高导电性、对电解质的催化能力、透明性和柔性等特点受到广泛关注。以含PEDOT或掺杂PEDOT对电极的DSSC为对象,阐述了PEDOT对电极的制备方法,并总结了近几年PEDOT作为DSSC对电极的研究进展。在此基础上,提出未来在电池效率突破研究中应以原位聚合法制备PEDOT对电极为主,以及在大规模工业化生产中应以物理涂覆法为主的观点,为PEDOT对电极DSSC的研究提供依据。     

导电聚合物纳米线的制备及气敏性能研究

首次采用简单的浸润多孔氧化铝(AAO)模板法制备了导电聚合物聚-3,4-乙烯二氧噻吩(PE-DOT)纳米线.导电聚合物溶液浸润AAO模板后,PEDOT吸附于孔道壁并进一步聚合生成导电聚合物纳米线.紫外-可见光-近红外光谱(UV-vis-NIR spec-trum)分析表明生成的纳米线处于掺杂态.采用四探针仪分析了导电聚合物纳米线的导电性能,结果显示纳米线电导率相比普通PEDOT材料有数量级增加,且表现出良好的掺杂/脱掺杂能力.研究了导电聚合物纳米线的气体敏感性能,发现其对挥发性醇类,尤其对甲醇在较低浓度下表现出优异的敏感性,对5×10-6甲醇气体的响应时间约为10～20s,测试可重复性超过20次,达到饱和吸附时的气体浓度明显大于普通PEDOT材料.表明PEDOT纳米线不仅提供了较大表面积供气体分子吸附,而且纳米线中导电通道取向一致,从而体现出较好的气体敏感性能.     

PSS-VS共聚物掺杂PEDOT的合成与表征

以苯乙烯磺酸钠(SSS)和乙烯磺酸钠(SVS)的共聚物PSS-VS为掺杂剂,过硫酸铵(APS)为氧化剂,采用化学氧化法制备了PEDOT/PSS-VS分散体,研究了PSS-VS的共聚比、分子量和用量等因素对PEDOT/PSS-VS导电性能及平均粒径的影响,分析了PEDOT/PSS-VS粒子形成过程。结果表明,SSS/SVS共聚摩尔比为5/5,单体与APS摩尔比为60时制得的PSS-VS掺杂PEDOT具有较好的导电性和分散稳定性,SO3-/EDOT=2,APS/EDOT=1.5,PEDOT/PSS-VS固含量为2.8%时制得的PEDOT/PSS-VS电导率可达11.74S/cm,分散体平均粒径为447nm。     

山梨醇掺杂对PVA/PEDOT∶PSS共混纤维结构和导电性能的影响

为改善PVA/PEDOT∶PSS共混纤维的导电性能,采用湿法纺丝的方法,通过向PVA/PEDOT∶PSS混合纺丝液中添加山梨醇,制备出经山梨醇掺杂的PVA/PEDOT∶PSS共混纤维。采用红外光谱分析仪(FTIR),高阻计,X射线衍射仪(XRD),显微共聚焦激光拉曼光谱仪,扫描电子显微镜(SEM),电子单纤维强力仪对共混纤维的结构与性能进行测试表征。通过对比分析掺杂前后共混纤维电导率的变化,探究了山梨醇掺杂对PVA/PEDOT∶PSS共混纤维结构和导电性能的影响。结果表明,山梨醇掺杂可以改善PVA/PEDOT∶PSS共混纤维的导电性能,掺杂质量分数为7%时,共混纤维电导率达到19.1S/cm。XRD结果显示,掺杂未改变PVA/PEDOT∶PSS共混纤维的结晶性能和聚集态结构;拉曼光谱显示,掺杂使得PEDOT的主要特征峰红移,PEDOT主链发生苯-醌转变;掺杂使得共混纤维的表面逐渐变得光滑;掺杂后,共混纤维的拉伸强度升高,断裂伸长降低。     

反离子聚合聚(3,4-乙烯二氧噻吩)薄膜的热电性能研究进展EI北大核心CSCD

反离子的选择对电化学聚合聚(3,4-乙烯二氧噻吩)(PEDOT)薄膜的结构和热电性能的影响备受关注,在已报道的聚合物薄膜中,PEDOT:聚(苯乙烯磺酸盐)(PSS)、PEDOT:甲苯磺酸盐(Tos)、PEDOT:高氯酸(ClO_(4))和PEDOT:三氟甲磺酸酯(OTf)等被广泛研究。文中综合分析了不同类型反离子对PEDOT薄膜热电性能的应用研究,重点阐述了PEDOT:PSS和PEDOT:Tos提高热电性能的工艺方法,PEDOT:PSS薄膜具有高电导率、可水处理和热稳定性高等特点,二次掺杂、化学去掺杂和连续处理工艺能有效提高其热电性能,但是PSS有亲水性的限制;而Tos具有疏水性,且PEDOT:Tos薄膜能够有效平衡赛贝克系数和电导率的关系;其它的PEDOT:ClO_(4)和PEDOT:OTf等薄膜对热电性能也起到了一定的促进作用。最后,展望了反离子聚合PEDOT薄膜作为柔性热电器件和可穿戴电子器件的开发和实际应用。对进一步研究新的反离子聚合具有一定的参考价值。     

基于灰色理论的掺杂态导电聚苯胺的制备及导电性能研究

以苯胺(An)为单体,氨基磺酸(SA)为掺杂剂,过硫酸铵(APS)为氧化剂,采用化学氧化聚合法合成了掺杂态导电聚苯胺。考察了n(苯胺)/n(掺杂剂)、n(苯胺)/n(氧化剂)和反应时间对聚苯胺电导率的影响。结果表明,当n(An)∶n(SA)∶n(APS)=1∶6∶0.4、反应时间为6h时,聚苯胺的电导率最高达到0.87S/cm。进一步利用灰色关联分析,定量地分析了各因素对掺杂态导电聚苯胺电导率的影响程度,得出了各因素影响电导率的大小顺序为掺杂剂、氧化剂、反应时间。并以氨基磺酸的添加量为基本建立了掺杂态导电聚苯胺电导率的灰色预测模型(灰色离散Verhulst模型),预测了氨基磺酸不同添加量下的电导率,平均预测精度为97.25%。结果证明,灰色系统理论在掺杂态导电聚苯胺的电导率的预测中是可行的。     

电化学沉积法制备PEDOT/PEDOT∶PSS基柔性纳米纤维膜及其热电性能

通过静电纺丝技术制备柔性热电薄膜是一种非常可行的方法,制得的纳米纤维会随机交叉排列形成多孔结构。该结构不仅可以增强薄膜的变形能力、柔性和延展性,还可以增加纳米纤维膜中低热导率的非流动空气的含量,有利于降低纳米纤维膜的导热系数,然而目前对于静电纺丝在柔性热电领域应用的相关研究非常少。本工作通过静电纺丝技术制备了具有良好自支撑性和柔性的聚(3,4-乙烯二氧噻吩)∶聚对苯乙烯磺酸钠(PEDOT∶PSS)基纳米纤维膜,并结合电化学聚合法在该纳米纤维表面沉积了PEDOT导电层,得到了PEDOT/PEDOT∶PSS基热电纳米纤维膜。研究发现,聚合电位和单体浓度对热电纳米纤维膜的导电率有很大影响,最终在聚合电位为1. 5 V、单体浓度为0. 03 mol/L时,电导率和塞贝克系数分别为9. 582 S·cm~(-1)和26. 7μV·K~(-1),最优PF值可达0. 68μW·m~(-1)·K~(-2)。     

On the mechanism of conductivity enhancement in plasma treated poly(3,4-ethylenedioxythiophene) films

The conductive poly(3,4-ethylenedioxythiophene): p-toluene sulfonate (PEDOT : PTS) films were prepared by gas-phase polymerization using CVD technique. PEDOT : PTS films with better electrical performance were produced by the additional doping with O₂ plasma after vapor phase polymerization. The mechanism for this conductivity enhancement is studied through surface structural analyses using Raman and X-ray photoelectron spectroscopy (XPS). The increase in conductivity is likely to be due to the generation of new functional groups such as carboxyl and hydroxyl groups that are acted as a dopant and the removal of the impurities on PEDOT: PTS surface with plasma treatment.     

Ultrahigh‐Conductivity Polymer Hydrogels with Arbitrary Structures

A poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) hydrogel is prepared by thermal treatment of a commercial PEDOT:PSS (PH1000) suspension in 0.1 mol L^?1 sulfuric acid followed by partially removing its PSS component with concentrated sulfuric acid. This hydrogel has a low solid content of 4% (by weight) and an extremely high conductivity of 880 S m^?1. It can be fabricated into different shapes such as films, fibers, and columns with arbitrary sizes for practical applications. A highly conductive and mechanically strong porous fiber is prepared by drying PEDOT:PSS hydrogel fiber to fabricate a current‐collector‐free solid‐state flexible supercapacitor. This fiber supercapacitor delivers a volumetric capacitance as high as 202 F cm^?3 at 0.54 A cm^?3 with an extraordinary high‐rate performance. It also shows excellent electrochemical stability and high flexibility, promising for the application as wearable energy‐storage devices.     

乙腈对环己烷单体溶液中沉降聚合聚3,4-乙撑二氧噻吩涂层结构与光电性能的影响EI北大核心CSCD

为利用溶剂化效应来优化液相沉降聚合聚3,4-乙撑二氧噻吩(PEDOT)的结构和光电性能,将吸附Fe(OTs)3的聚对苯二甲酸乙二醇酯(PET)膜悬于含乙腈的EDOT环己烷溶液中,于60℃原位合成PEDOT涂层。以紫外-可见吸收光谱、X射线光电子能谱分析所合成PEDOT的共轭链结构和掺杂度,以四探针测量表面电阻,研究乙腈含量对合成PEDOT结构与性能的影响。当乙腈体积分数为0.05%时,添加的乙腈能抑制短共轭链的生成,提高掺杂度,在降低表面电阻的同时,改善透光率。乙腈体积分数在0.24%以内时,PEDOT的导电性随乙腈体积分数的上升而增加。当乙腈体积分数超过0.7%时,PEDOT中短共轭链数目增加,光电性能下降。当乙腈体积分数为8%时,由于吸附的Fe(OTs)_3溶解太快,无法在PET表面合成导电PEDOT膜。乙腈体积分数为0.24%时,获得的PEDOT膜的表面电阻可达174Ω,透光率80%,粘附力为5B级。     

Fabrication of flexible conductive films derived from poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) on the nonwoven fabrics substrate

In this research, conducting poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonic acid) (PEDOT:PSS) aqueous dispersion was synthesized at first via chemical oxidative polymerization and followed by mixing it with poly(styrene-r-butyl acrylate) P(St-BA) aqueous latex, creating a conductive material with outstanding stretchability. The elastic conductive composite were then film formed on the glass and poly(ethylene terephthalate) (PET) nonwoven fabric substrate by spin coating and dip coating, respectively. Composite films with various contents of PEDOT:PSS polymer (10–100 wt.%) had been prepared. From the conductivity measurements, the conductivity was still kept as high as 88 S cm⁻¹ even the PEDOT:PSS content was lowered to 10 wt.%. Furthermore, the elasticity of conductive films on the PET-nonwoven fabric substrate was evaluated by the 180° bending test repeating 100 times. With introducing soft P(St-BA) material in the PEDOT:PSS phase, the surface resistance increased merely 3–6 times after bending 100 times, while the surface resistance for pure PEDOT:PSS film could reach 18–20 times.     

Multiwall carbon nanotube and poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) composite films for transistor and inverter devices

Highly conductive multiwalled carbon nanotube (MWNT)/Poly(3,4-ethylenedioxythiophene) polymerized with poly(4-styrenesulfonate) (PEDOT:PSS) films were prepared by spin coating a mixture solution. The solution was prepared by dispersing MWNT in the PEDOT:PSS solution in water using ultrasonication without any oxidation process. The effect of the MWNT loading in the solution on the film properties such as surface roughness, work function, surface energy, optical transparency, and conductivity was studied. The conductivity of MWNT/PEDOT:PSS composite film was increased with higher MWNT loading and the high conductivity of MWNT/PEDOT:PSS films enabled them to be used as a source/drain electrode in organic thin film transistor (OTFT). The pentacene TFT with MWNT/PEDOT:PSS S/D electrode showed much higher performance with mobility about 0.2 cm2/(V s) and on/off ratio about 5 × 10? compared to that with PEDOT:PSS S/D electrode (～0.05 cm2/(V s), 1 × 10?). The complementary inverters exhibited excellent characteristics, including high gain value of about 30.     

Enhancement of poly(3,4-ethylenedioxy thiophene)/poly(styrene sulfonate) properties by poly(vinyl alcohol) and doping agent as conductive nano-thin film for electronic application

In this work, the integration of the useful concepts of polymer blending and doping agent to simultaneously improve various properties of poly(3,4-ethylene dioxy thiophene) poly(styrene sulfonate) (PEDOT:PSS) nano-thin films was shown. According to the polymer-blending concept, insulating poly(vinyl alcohol) (PVA) has a good deal of potential to be utilized as a filler to improve the critical properties of the PEDOT:PSS matrix, especially conductivity, wettability, and thermal and mechanical properties. At the appropriate amount of PVA, 0.08 wt%, it acts as a binder to improve the connection network between PEDOT:PSS chains, leading to a maximum conductivity of 1.18 S/cm, and also providing a good contact angle of 8.8°. The transmission of the films decreased with increasing PVA content; however, all specimens still showed excellent transmittance values of more than 80 %. The thermal stability and the resistance to abrasion of the nano-thin conductive films were improved by strong covalent bonds between PVA and PSS, which were verified by TGA and a scratching test, respectively. In addition, the relationship of PEDOT:PSS properties versus various amounts of insulating PVA for practical usage for specific electronic fields were shown. Use of the doping agent quinoxaline was aimed to particularly enhance the conductivity of PEDOT:PSS. The highest conductivity (2.75 S/cm) was achieved when 0.5 wt% quinoxaline was added into 0.08 wt% PVA/PEDOT:PSS while the other properties were not significantly altered.     

Strong and stable doping of carbon nanotubes and graphene by MoOx for transparent electrodes

MoO(x) has been used for organic semiconductor doping, but it had been considered an inefficient and/or unstable dopant. We report that MoO(x) can strongly and stably dope carbon nanotubes and graphene. Thermally annealed MoO(x)-CNT composites can form durable thin film electrodes with sheet resistances of 100 Ω/sq at 85% transmittance plain and 85 Ω/sq at 83% transmittance with a PEDOT:PSS adlayer. Sheet resistances change less than 10% over 20 days in ambient and less than 2% with overnight heating to 300 °C in air. The MoO(x) can be easily deposited either by thermal evaporation or from solution-based precursors. Excellent stability coupled with high conductivity makes MoO(x)-CNT composites extremely attractive candidates for practical transparent electrodes.     

提高聚(3,4-乙撑二氧噻吩)∶聚苯乙烯磺酸电导率的最新研究进展

随着能源危机和环境污染问题的日益严峻,近年来热电材料的研究越来越受到人们的关注。聚(3,4-乙撑二氧噻吩)∶聚苯乙烯磺酸(PEDOT∶PSS)被认为是热电性能最好的有机热电材料之一。PEDOT∶PSS具备好的成膜性、高的透明性、优异的电导可控性以及热稳定性。系统地综述了提高PEDOT∶PSS电导率的一些物理、化学方法,探讨了其电导率增强的机理以及介绍了其目前最新的应用情况。预期未来具有高电导率和高透明性的PEDOT∶PSS薄膜材料的研究将得到突破性发展。     

An Efficiently Doped PEDOT:PSS Ink Formulation via Metastable Liquid−Liquid Contact for Capillary Flow-Driven,Hierarchically and Highly Conductive Films

With commercial electronics transitioning toward flexible devices, there is a growing demand for high-performance polymers such as poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) (PEDOT:PSS). Previous breakthroughs in promoting the conductivity of PEDOT:PSS, which mainly stem from solvent-treatment and transfer-printing strategies, remain as inevitable challenges due to the inefficient, unstable, and biologically incompatible process. Herein, a scalable fabrication of conducting PEDOT:PSS inks is reported via a metastable liquid−liquid contact (MLLC) method, realizing phase separation and removal of excess PSS simultaneously. MLLC-doped inks are further used to prepare ring-like films through a compromise between the coffee-ring effect and the Marangoni vortex during evaporation of droplets. The specific control over deposition conditions allows for tunable ring-like morphologies and preferentially interconnected networks of PEDOT:PSS nanofibrils, resulting in a high electrical conductivity of 6,616 S cm⁻¹ and excellent optical transparency of the film. The combination of excellent electrical properties and the special morphology enables it to serve as electrodes for touch sensors with gradient pressure sensitivity. These findings not only provide new insight into developing a simple and efficient doping method for commercial PEDOT:PSS ink, but also offer a promising self-assembled deposition pattern of organic semiconductor films, expanding the applications in flexible electronics, bioelectronics as well as photovoltaic devices.