Conducting block copolymer for simple micro- to nanopatterns

To use conducting polymers as substitutes for metals and conventional semiconductors in device fabrication, a cost-effective process for the reproducible deposition of the conducting polymers is needed. In this letter, we report a simple solution casting method for the fabrication of micro- to nanopatterns using the conducting block copolymer, poly(thiophene-block-ethyleneoxide), which shows rectifying characteristics dependent on the pattern width.     

Oxygenation of conducting polymers facilitated by structure-breaking anions

Conducting polymers are an interesting class of materials that can be tuned to have a range of properties through counterion doping. For most conducting polymers, the insertion of anions (the doping process) leads to the formation of carbocations (positive charge carriers) along the conjugated polymer backbone. In this research, we report on a scenario that arises where certain (commonly used) anions in water induce oxygenation of the conducting polymers heteroatom. This is in contrast to the widely reported doping process, and the recently reported hydrolysis of conducting polymers. We observe that the transition between these different conducting polymer-interactions/reactions is well described by the concept of structure-making and structure-breaking anions. Poly(3,4-propylenedioxy thiophene dimethyl) (PProDOT-Me₂), polypyrrole (PPy), and poly(3,4-ethylenedioxy thiophene) (PEDOT) thin films are exposed to a range of anions in water. Both PProDOT-Me₂ and PPy are susceptible to oxygenation, while in contrast PEDOT is doped, when exposed to structure-breaking anions. All the polymers show hydrolysis for structure-making anions. The knowledge of the interaction and/or reaction of conducting polymers with anions in water is not only critical to their application in devices for aqueous environments (i.e., sensing), but also for their processing and fabrication using water.     

聚合物场效应晶体管材料及其器件

导电聚合物因为可以大面积成膜、器件制作工艺简单,近年来在有机场效应晶体管的研究中受到越来越多的关注。有的聚合物场效应晶体管其性能已经可以和无定型硅晶体管相比拟。本文回顾了聚合物场效应晶体管的发展历程,概述了聚合物场效应晶体管的材料、器件制作、性能及工作机理。同时,对聚合物场效应晶体管的发展前景和目前存在的问题作了简单的总结。     

聚合物场效应晶体管材料及其器件

导电聚合物因为可以大面积成膜、器件制作工艺简单,近年来在有机场效应晶体管的研究中受到越来越多的关注.有的聚合物场效应晶体管其性能已经可以和无定型硅晶体管相比拟.本文回顾了聚合物场效应晶体管的发展历程,概述了聚合物场效应晶体管的材料、器件制作、性能及工作机理.同时,对聚合物场效应晶体管的发展前景和目前存在的问题作了简单的总结.     

π‐Conjugated Microporous Polymer Films: Designed Synthesis,Conducting Properties,and Photoenergy Conversions

Conjugated microporous polymers are a unique class of polymers that combine extended π‐conjugation with inherent porosity. However, these polymers are synthesized through solution‐phase reactions to yield insoluble and unprocessable solids, which preclude not only the evaluation of their conducting properties but also the fabrication of thin films for device implementation. Here, we report a strategy for the synthesis of thin films of π‐conjugated microporous polymers by designing thiophene‐based electropolymerization at the solution–electrode interface. High‐quality films are prepared on a large area of various electrodes, the film thickness is controllable, and the films are used for device fabrication. These films are outstanding hole conductors and, upon incorporation of fullerenes into the pores, function as highly efficient photoactive layers for energy conversions. Our film strategy may boost the applications in photocatalysis, energy storage, and optoelectronics.     

π‐Conjugated Microporous Polymer Films: Designed Synthesis,Conducting Properties,and Photoenergy Conversions

Conjugated microporous polymers are a unique class of polymers that combine extended π‐conjugation with inherent porosity. However, these polymers are synthesized through solution‐phase reactions to yield insoluble and unprocessable solids, which preclude not only the evaluation of their conducting properties but also the fabrication of thin films for device implementation. Here, we report a strategy for the synthesis of thin films of π‐conjugated microporous polymers by designing thiophene‐based electropolymerization at the solution–electrode interface. High‐quality films are prepared on a large area of various electrodes, the film thickness is controllable, and the films are used for device fabrication. These films are outstanding hole conductors and, upon incorporation of fullerenes into the pores, function as highly efficient photoactive layers for energy conversions. Our film strategy may boost the applications in photocatalysis, energy storage, and optoelectronics.     

Overview on conducting polymer in energy storage and energy conversion system

Polymer-based electrochemical devices such as supercapacitor, battery, and fuel cell have been developed and advanced for energy related application. In this regard, conducting polymers own several tunable characteristics for energy conversion and energy storage relevance. Consequently, efficient, reliable, low cost, conducting, stable, and environment friendly energy systems have been developed using conducting polymers. To enhance the efficiency and commercialization of energy systems, design, structure, composition, and fabrication technique used for conducting polymers and related composite have been focused. Challenges and future trend associated with current state of the art conducting polymer materials in supercapacitor, battery, and fuel cell are highlighted.     

Patterning of conducting polymers using charged self-assembled monolayers

We introduce a new approach to pattern conducting polymers by combining oppositely charged conducting polymers on charged self-assembled monolayers (SAMs). The polymer resist pattern behaves as a physical barrier, preventing the formation of SAMs. The patterning processes were carried out using commercially available conducting polymers: a negatively charged PEDOT/PSS (poly(3,4-ethylene-dioxythiophene)/poly(4-stylenesulphonic acid)) and a positively charged polypyrrole (PPy). A bifunctional NH 2 (positively charged) or COOH (negatively charged) terminated alkane thiol or silane was directly self-assembled on a substrate (Au or SiO 2). A suspension of the conducting polymers (PEDOT/PSS and PPy) was then spin-coated on the top surface of the SAMs and allowed to adsorb on the oppositely charged SAMs via an electrostatic driving force. After lift-off of the polymer resist, i.e., poly(methyl methacrylate, PMMA), using acetone, the conducting polymers remained on the charged SAMs surface. Optical microscopy, Auger electron spectroscopy, and atomic force microscopy reveal that the prepared nanolines have low line edge roughness and high line width resolution. Thus, conducting polymer patterns with high resolution could be produced by simply employing charged bifunctional SAMs. It is anticipated that this versatile new method can be applied to device fabrication processes of various nano- and microelectronics.     

高分子对酶、抗体、DNA的修饰、固定化及其生物医学应用

为发展适于生物医用的生物功能高分子材料,本实验室近年来研究了可溶性高分子对L-天冬酰胺酶的修饰、纳米磁性高分子微粒对酶或抗体的固定化、亚微米高分子微球固定化碱性磷酸酶及其在DNA检测中的应用、高分子微球固定化酶的合成与性能、酶在导电高分子膜上的固定化及生物传感器制备等. 本文对此进行简要总结.     

Selective extraction of large-diameter single-wall carbon nanotubes with specific chiral indices by poly(9,9-dioctylfluorene-alt-benzothiadiazole)

Semiconducting single-wall carbon nanotubes (SWCNTs) having large diameters (d(t) > 1.3 nm) are successfully extracted in toluene by fluorene-based polymers. In particular, poly(9,9-dioctylfluorene-alt-benzothiadiazole) shows excellent selectivity for (15,4) SWCNTs. Although the importance of structural matching between the fluorene backbone and the tube surface has already been discussed, the present photoluminescence studies reveal that matching the energy levels between fluorene-based polymers and SWCNTs is crucial for selective nanotube extractions.     

Graphene and its nanocomposites used as an active materials for supercapacitors

This review article investigates the hot topics by presenting the latest advances on graphene-based nanostructures for supercapacitors. In literature, many scientists have studied the nanomaterials and combination of conducting polymers in supercapacitor (SC) devices. The main aim of this review article is to present the higher capacitance, and higher power and energy density performances of the SC devices, which includes the active materials of carbon-based materials, metal oxides, conducting polymers, nanocomposites, etc. Many conventional techniques have already been used such as photolithography, inkjet printing, etc. Each of these methods has specific advantages and some drawbacks, with some working better in different environments. Among various nanoscaled materials, nanocrystal oxides of transition metals play an important role in advanced materials development. In addition to design of active material, symmetric and asymmetric supercapacitor device fabrication is also directly effect to obtain a higher capacitance, energy and power density performances. Therefore, this review article focuses on supercapacitor technology in new developments, such as design of active materials, device fabrication, etc.     

导电聚合物的纳米结构及其在生物医学领域的应用

由于表面效应、小尺寸效应和量子效应,使纳米结构的导电聚合物材料与传统聚合物材料相比,显示出更优越的性能。基于神经组织对电场和电刺激敏感性,使得导电聚合物纳米材料在生物医学应用方面很有前景。本文综述了纳米结构的导电聚合物的合成方法,及其在生物医学领域的应用。合成方法主要关注于硬模板法、软模板法和无模板自组装法,以及这些方法中导电聚合物纳米结构的形成机理。总结了具有纳米结构的导电聚合物,如纳米颗粒、纳米纤维和纳米管等作为神经电极涂层材料和生物传感器等方面的应用。     

Extraction of (9,8) Single‐Walled Carbon Nanotubes by Fluorene‐Based Polymers

Selective polymer wrapping is a promising approach to obtain high‐chiral‐purity single‐walled carbon nanotubes (SWCNTs) needed in technical applications and scientific studies. We showed that among three fluorene‐based polymers with different side‐chain lengths and backbones, poly[(9,9‐dihexylfluorenyl‐2,7‐diyl)‐co‐(9,10‐anthracene)] (PFH‐A) can selectively extract SWCNTs synthesized from the CoSO₄/SiO₂ catalyst, which results in enrichment of 78.3 % (9,8) and 12.2 % (9,7) nanotubes among all semiconducting species. These high‐chiral‐purity SWCNTs may find potential applications in electronics, optoelectronics, and photovoltaics. Furthermore, molecular dynamics simulations suggest that the extraction selectivity of PFH‐A relates to the bending and alignment of its alkyl chains and the twisting of its two aromatic backbone units (biphenyl and anthracene) relative to SWCNTs. The strong π–π interaction between polymers and SWCNTs would increase the extraction yield, but it is not beneficial for chiral selectivity. Our findings suggest that the matching between the curvature of SWCNTs and the flexibility of the polymer side chains and the aromatic backbone units is essential in designing novel polymers for selective extraction of (n,m) species.     

Chemically assisted directed assembly of carbon nanotubes for the fabrication of large-scale device arrays

We report the directed assembly of single-walled carbon nanotubes (SWCNTs) at lithographically defined positions on gate oxide surfaces, allowing for the high yield ( approximately 90%) and parallel fabrication of SWCNT device arrays. SWCNTs were first chemically functionalized through diazonium chemistry with a hydroxamic acid end group that both renders the SWCNTs water-soluble and discriminately binds the SWCNTs to basic metal oxide surfaces (i.e., hafnium oxide (HfO2)). The functionalized SWCNTs are then assembled from an aqueous solution into narrow trenches etched into SiO2 films with HfO2 at the bottom. The side walls of the patterned trenches induce alignment of the SWCNTs along the length of the trenches. Heating the structures to 600 degrees C removes the organic moieties, leaving pristine SWCNTs as evidenced by Raman spectroscopy and electrical measurements. Palladium source-drain electrodes deposited perpendicular to the trench length readily contact the ends of the aligned SWCNTs. The resultant devices exhibit the electrical performance expected for SWCNT devices, with no performance deterioration as a result of the placement process. This technique allows for the directed assembly and alignment of SWCNTs over a large area and results in a high yield of working devices, presenting a promising path toward large-scale SWCNT device integration.     

高分子功能材料图案化制备及其在光电领域的应用

基于半导体高分子功能材料的新型光电器件因其兼容性好、成本低、加工处理方便等特点逐渐走入人们的视野.加工集成高性能高分子光电器件需要用到可控图案化技术,这也将成为未来物联网、光通信、智能社会的基础核心技术.近年来,许多致力于此方面的研究取得了重要的成果.本文总结了各类高分子材料图案化技术,包括光刻法、模具诱导法、印刷法、浸润性调控组装法的技术特点,然后归纳了高分子图案化技术在场效应晶体管、光电探测器、气体传感器、电致发光二极管、光伏器件等光电器件领域的研究进展,最后对未来这一领域发展的挑战与机遇进行了展望.     

Phenylboronate‐diol crosslinked polymer/SWCNT hybrid gels with reversible sol–gel transition

This work demonstrates the successful incorporation of functionalized single‐walled carbon nanotubes (f‐SWCNTs) into the phenylboronate‐diol crosslinked polymer gel to create a hybrid system with reversible sol–gel transition. The phenylboronic acid‐containing and diol‐containing polymers were first separately prepared by the reversible addition–fragmentation chain transfer polymerization. Covalent functionalization of single‐walled carbon nanotubes (SWCNTs) with an azide‐derivatized, diol‐containing polymer was then accomplished by a nitrene addition reaction. Subsequently, the hybrid gels were prepared by crosslinking the mixture of f‐SWCNTs and diol‐containing polymer with the phenylboronic acid‐containing polymer. The hybrid gel has been characterized by scanning electron microscopy (SEM) and rheological analysis. The SEM measurement demonstrated a homogeneous dispersion of f‐SWCNTs within the gel matrices. Rheological experiments also demonstrated that the hybrid gel exhibited storage moduli significantly higher than those of the native gel obtained from the phenylboronic acid‐containing and diol‐containing polymers. The hybrid gel can be switched into their starting polymer (f‐SWCNTs) solutions by adjusting the pH of the system. Moreover, the hybrid gel revealed a self‐healing property that occurred autonomously without any outside intervention. By employing this dynamic character, it is possible to regenerate the used gel, and thus, it has the potential to perform in a range of dynamic or bioresponsive applications Copyright © 2013 John Wiley & Sons, Ltd.     

Electrosynthetically patterned conducting polymer films for investigation of neural signaling

The ion-mediated conduction and versatility of device fabrication of conducting polymers provide a route to the study of neural signaling. Patterned junctions of conducting polypyrrole have been electropolymerized on commercially available microelectrode arrays, with typical dimensions 200 mum between electrodes, each electrode being 30 mum in diameter. Tetrabutylammonium perchlorate or sodium p-toluenesulfonate were used as electrolyte/counterion in the organic solvent. Individual polypyrrole junctions, when synthesized and connected in a three-electrode configuration, exhibit current-switching behavior analogous to neural weighting. Junctions copolymerized with thiophene exhibit current rectification and the nonlinear current-voltage behavior requisite for complex neural systems (i.e., the activation function).     

导电聚合物

导电聚合物是20世纪70年代发展起来的一个研究领域,因其诱人的应用前景受到广泛重视,本文介绍了导电聚合物的发展和发展历史,综述了导电聚合物的结构和掺杂特征,制造方法,电导和电化学特性及其本征态共轭聚合物的光电特性,对导电聚合物当前的研究热点和应用前景进行了讨论。     

Charge transport and structure in semimetallic polymers

Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low‐cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi‐metallic conducting polymer poly(3,4‐ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm²/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X‐ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer‐based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 97–104     

Polypyrimidine/SWCNTS composite comprising Pt nanoparticles: Possible electrocatalyst for fuel cell

The poly(9,9-dioctyl fluorine-alt-2-amino-4,6-pyrimidine) (oligomer) is used as an effective dispersant for single walled carbon nanotubes (SWCNTs) and generates stable SWCNTs hybrid after elimination of the excess polymer. The covered polymers immobilized Pt nanoparticles onto the surface of single-walled carbon nanotubes (SWCNTs) by coordination between Pt and polymer and the amount of the loaded Pt on the hybrid was calculated to be 38.5 wt %. The average diameter of the Pt nanoparticles on the SWCNTs were about ～4–5 nm and have a moderate electrochemically active surface area of 40.5 m²/g. These studies strongly imply the possible application of novel pyrimidine/carbon materials as catalyst supports in the electrodes of fuel cells.