Emulsion synthesis of nanoparticles containing PEDOT using conducting polymeric surfactant: Synergy for colloid stability and intercalation doping

Poly(3,4‐ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS) is a widely used conductive aqueous dispersion synthesized by using emulsion polymerization method. To further enhance its solution processability and conductivity of PEDOT derivatives, we proposed to replace the nonconductive PSS with conductive poly[2‐(3thienyl)‐ethoxy‐4‐butylsulfonate] (PTEB) as surfactant for the emulsion polymerization of PEDOT. The reaction involved colloid stabilization and doping in one step, and yielded PEDOT:PTEB composite nanoparticles with high electrical conductivity. Contrary to its counterpart containing nonconductive surfactant, PEDOT: PTEB showed increasing film conductivity with increasing PTEB concentration. The result demonstrates the formation of efficient electrical conduction network formed by the fully conductive latex nanoparticles. The addition of PTEB for EDOT polymerization significantly reduced the size of composite particles, formed stable spherical particles, enhanced thermal stability, crystallinity, and conductivity of PEDOT:PTEB composite. Evidence from UV–VIS and FTIR measurement showed that strong molecular interaction between PTEB and PEDOT resulted in the doping of PEDOT chains. X‐ray analysis further demonstrated that PTEB chains were intercalated in the layered crystal structure of PEDOT. The emulsion polymerization of EDOT using conducting surfactant, PTEB demonstrated the synergistic effect of PTEB on colloid stability and intercalation doping of PEDOT during polymerization resulting in significant conductivity improvement of PEDOT composite nanoparticles. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2536–2548, 2008     

Metal-like Charge Transport in PEDOT(OH) Films by Post-processing Side Chain Removal from a Soluble Precursor Polymer

Herein, a route to produce highly electrically conductive doped hydroxymethyl functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) films, termed PEDOT(OH) with metal-like charge transport properties using a fully solution processable precursor polymer is reported. This is achieved via an ester-functionalized PEDOT derivative [PEDOT(EHE)] that is soluble in a range of solvents with excellent film-forming ability. PEDOT(EHE) demonstrates moderate electrical conductivities of 20–60 S cm⁻¹ and hopping-like (i.e., thermally activated) transport when doped with ferric tosylate (FeTos₃). Upon basic hydrolysis of PEDOT(EHE) films, the electrically insulative side chains are cleaved and washed from the polymer film, leaving a densified film of PEDOT(OH). These films, when optimally doped, reach electrical conductivities of ≈1200 S cm⁻¹ and demonstrate metal-like (i.e., thermally deactivated and band-like) transport properties and high stability at comparable doping levels.     

导电高分子的最近进展

因为导电高分子结合了金属与塑料的优点,他们一直受到很大的关注。但是他们的应用受到一些因素的影响,包括他们的电学性质,稳定性和可加工性。近来,导电高分子的性能得到很大的提高。他们在许多领域的重要应用被论证,比如透明电极,可拉伸电极,神经界面,热电转换和能量储存。这篇文章简单综述了导电高分子的电导提高和它们在热电转换,超级电容器和电池的应用。     

Highly Conductive PEDOT:PSS Films with 1,3‐Dimethyl‐2‐Imidazolidinone as Transparent Electrodes for Organic Light‐Emitting Diodes

Highly conductive poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films as transparent electrodes for organic light‐emitting diodes (OLEDs) are doped with a new solvent 1,3‐dimethyl‐2‐imidazolidinone (DMI) and are optimized using solvent post‐treatment. The DMI doped PEDOT:PSS films show significantly enhanced conductivities up to 812.1 S cm⁻¹. The sheet resistance of the PEDOT:PSS films doped with DMI is further reduced by various solvent post‐treatment. The effect of solvent post‐treatment on DMI doped PEDOT:PSS films is investigated and is shown to reduce insulating PSS in the conductive films. The solvent posttreated PEDOT:PSS films are successfully employed as transparent electrodes in white OLEDs. It is shown that the efficiency of OLEDs with the optimized DMI doped PEDOT:PSS films is higher than that of reference OLEDs doped with a conventional solvent (ethylene glycol). The results present that the optimized PEDOT:PSS films with the new solvent of DMI can be a promising transparent electrode for low‐cost, efficient ITO‐free white OLEDs.

     

Investigation of the doping efficiency of poly(styrene sulfonic acid) in poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) dispersions by capillary electrophoresis

CE can efficiently separate poly(3,4‐ethylenedioxythiophene)/poly(styrene sulfonic acid) (PEDOT/PSS) complexes and free PSS in dispersions and can be used to estimate the degree of PSS doping. We investigated the doping efficiency of PSS on PEDOT in dispersions using CE and its effect on the conductivity of the resulting PEDOT/PSS films. Results of this study indicate that dispersions containing 1:2.5–3 EDOT:PSS feed ratio (by weight) exhibiting 72–73% PSS doping generate highly processable and highly conductive films. Conductivity can be optimized by limiting the time of reaction to 12 h. At this point of the reaction, the PEDOT/PSS segments, appearing as broad band in the electropherogram, could still exist in an extended coil conformation favoring charge transport resulting in high conductivity. Above a threshold PEDOT length formed at reaction times longer than 12 h, the PEDOT/PSS complex, appearing as spikes in the electropherogram, most likely have undergone a conformational change to coiled core‐shell structure restricting charge transport resulting in low conductivity. The optimal conductivity (5.2 S/cm) of films from dispersions synthesized for 12 h is significantly higher than those from its commercial equivalent Clevios P and other reported values obtained under similar conditions without the addition of codopants.     

修饰Langmuir-Blodget膜法制备聚(3,4-亚乙基二氧噻吩)薄膜结构和导电性能的研究

采用修饰Langmuir-Blodget(LB)膜法以二十烷酸(AA)LB膜为模板,通过3,4-亚乙基二氧噻吩(EDOT)单体在LB膜亲水基团间聚合,制备了二十烷酸/聚(3,4-亚乙基二氧噻吩)(AA/PEDOT)复合LB膜.UV-Vis、FTIR和XPS分析表明EDOT在多层膜中有效聚合,生成了PEDOT导电聚合物;X射线衍射(XRD)和二次离子质谱(SIMS)分析表明薄膜具有较好的层状有序结构,进一步研究发现EDOT在AA多层膜中的聚合破坏了原有LB膜的有序性,这可能与聚合过程对层状结构产生的破坏作用有关;采用四探针仪及半导体测试仪研究了薄膜导电性能,发现AA/PEDOT多层膜的电导率随处理时间的变化产生突变,这与多层膜中导电通道的"逾渗"有关,在有效导电网络连通后电导率发生了突变.测试结果还表明AA层和PEDOT层之间具有较为明显的界面,PEDOT显示出较好的定域性,薄膜具有很好的层状有序结构.     

导电二氧化钛的合成研究

综述了导电TiO2的合成方法,包括本征TiO2高温电导、磁控溅射制备纳米导电膜、表面掺杂制备TiO2压敏电阻、表面包覆制备导电粉体、晶面离子注入改性、等离子喷涂制备导电涂层等方面。并介绍了导电原理、影响因素和用途。参考文献35篇。     

Micro-patterning of vapor-phase polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) using ink-jet printing/soft lithography

Highly conductive and transparent poly(3,4-ethylenedioxythiophene) (PEDOT) thin films can be prepared effectively via vapor-phase polymerization (VPP) with the addition of imidazole (Im) based derivatives. The addition of Im that has one and/or two alkyl substituents significantly improved the electrical conductivity of PEDOT thin films. In an effort to develop a facile PEDOT micro-patterning method, we investigated ink-jet printing and soft lithography. The procedure of oxidant patterning with a weak base followed by VPP of a 3,4-ethylenedioxythiophene (EDOT) monomer provides an effective and simple method for micro-patterning of an intrinsic conductive polymer (ICP).     

Polymer Optoelectronic Devices with High‐Conductivity Poly(3,4‐Ethylenedioxythiophene) Anodes

Abstract

The conductivity of poly(3,4‐ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) film can be enhanced by more than two orders in magnitude by adding a compound with two or more polar groups, such as ethylene glycol (EG), meso‐erythritol (IUPAC name: 1,2,3,4‐tetrahydroxybutane), or 2‐nitroethanol, into the PEDOT:PSS aqueous solution. The mechanism of the increase in conductivity for PEDOT:PSS has been studied using Raman spectroscopy and atomic force microscope (AFM). Here we propose that the change in conductivity is due to the conformational change of PEDOT chains in the film. In untreated PEDOT:PSS films, coil, linear, or expanded‐coil conformations of the PEDOT chains may be present. In treated PEDOT:PSS films, the linear or expanded‐coil conformations may becomes the dominant form for PEDOT chains. This conformational change results in the enhancement of charge‐carrier mobility in the film and leads to enhanced conductivity. The high‐conductivity PEDOT:PSS film is ideal as the electrode for polymer optoelectronic devices. In this article, we report on the fabrication of polymer light‐emitting diodes (PLEDs) and photovoltaic cells (PVs) made using a highly conductive form of PEDOT:PSS as anode, and we demonstrate its performance relative to that of similar device using indium‐tin oxide (ITO) as the anode.     

Secondary doping in poly(3,4‐ethylenedioxythiophene):Poly(4‐styrenesulfonate) thin films

The electrical and structural properties of poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS) thin films deposited from aqueous dispersion using different concentrations of selected secondary dopants are studied in detail. An improvement of the electrical conductivity by three orders of magnitude is achieved for dimethyl sulfoxide, sorbitol, ethylene glycol, and N,N‐dimethylformamide, and the secondary dopant concentration dependence of the conductivity exhibits almost identical behavior for all investigated secondary dopants. Detailed analysis of the surface morphology and Raman spectra reveals no presence of the secondary dopant in fabricated films, and thus the dopants are truly causing the secondary doping effect. Although the ratio of benzenoid and quinoid vibrations in Raman spectra is unaffected by doping, the phase transition in PEDOT:PSS films owing to doping is confirmed. Further analysis of temperature‐dependent conductivity reveals 1D variable range hopping (VRH) charge transport for undoped PEDOT:PSS, whereas highly conductive doped PEDOT:PSS films exhibit 3D VRH charge transport. We demonstrate that the charge ‐ hopping dimensionality change should be a fundamental reason for the conductivity enhancement. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1139–1146     

金属离子掺杂二氧化钛及水体光催化脱氮研究

采用溶胶-凝胶法制备了掺杂Ce³⁺、La³⁺、Ag⁺、Fe³⁺的TiO₂光催化剂,以考察其薄膜和粉体形式对水中无机氮的光催化去除效果和活性.用所制备的催化剂对含氨氮-亚硝酸氮的混合液进行了光催化脱氮研究.本文利用UV-Vis吸收光谱、XRD和TEM对催化剂进行了表征.同时,对影响TiO₂光催化效率的因素:如掺杂金属离子的种类、浓度、涂膜层数、反应液中有无Fe²⁺、不锈钢和玻璃载体、反应器的构型等进行了探讨,并对今后的研究进行展望.经过2 h紫外光照射反应,实验最佳脱氮效果:金属离子掺杂TiO₂薄膜型催化剂总氮去除率在30%左右,金属离子掺杂粉末型催化剂光催化最高总氮去除率可达41.7%.     

Fe3+掺杂TiO2光催化降解聚乙烯薄膜的研究

以快速溶胶-凝胶法制备了纳米TiO2光催化剂,并用Fe3 对其掺杂改性,在室温条件下,用于固相光催化降解聚乙烯(PE)包装薄膜的研究.对催化剂和薄膜进行了X衍射分析(XRD)、傅立叶红外光谱分析(FT-IR)、扫描电子显微镜(SEM)形貌观察.结果表明,60W紫外光辐射240h后,PE失重为8.43%,锐钛矿型纳米TiO2光催化剂使PE失重30.66%;用Fe3 掺杂后,0.5?2O3/TiO2、1.0?2O3/TiO2和2.0?2O3/TiO2分别使PE失重35.91%、20.72%和13.30%.光催化剂加速了PE的失重,碳链的断裂和光氧化腐蚀,在薄膜表面形成大量的坑洞,降解产物中的小分子量的石蜡含量明显增高.Fe3 掺杂有一个最佳量,0.5?2O3/TiO2光催化降解PE的活性最高.     

Fabrication and characterization of multi-metal co-doped titania films for a water-splitting reaction

Anchored visible-light-absorbing TiO(2) films have been synthesized by the layer-by-layer method on a quartz slide substrate as a new class of visible light-sensitive photocatalyst. UV-vis, XRD and XPS spectra show that W and Mn enter the TiO(2) lattices and partially substitute for Ti, and that W appears to have a solubility limit into the anatase structure. The Mn and W dopants cause new electronic states above the valence-band edge of pure TiO(2), and the new electronic states may be directly related to the visible-light absorption of doped TiO(2) films. A constant H(2) generation rate is obtained for long periods of time for all the investigated TiO(2) films, and the H(2) production rates for titania films doped with 0.74 at% W (relative to Ti) are 4.1 and 3.3 times higher than that of non-doped TiO(2) under UV and visible light, respectively, as the dopant atoms not only restrict the band gap to the visible region, but also facilitate the detrapping of charge carriers to the surface of the catalyst.     

Virus-Poly(3,4-ethylenedioxythiophene) Biocomposite Films

Virus-poly(3,4-ethylenedioxythiophene) (virus-PEDOT) biocomposite films are prepared by electropolymerizing 3,4-ethylenedioxythiophene (EDOT) in aqueous electrolytes containing 12 mM LiClO(4) and the bacteriophage M13. The concentration of virus in these solutions, [virus](soln), is varied from 3 to 15 nM. A quartz crystal microbalance is used to directly measure the total mass of the biocomposite film during its electrodeposition. In combination with a measurement of the electrodeposition charge, the mass of the virus incorporated into the film is calculated. These data show that the concentration of the M13 within the electropolymerized film, [virus](film), increases linearly with [virus](soln). The incorporation of virus particles into the PEDOT film from solution is efficient, resulting in a concentration ratio of [virus](film):[virus](soln) ≈ 450. Virus incorporation into the PEDOT causes roughening of the film topography that is observed using scanning electron microscopy and atomic force microscopy (AFM). The electrical conductivity of the virus-PEDOT film, measured perpendicular to the plane of the film using conductive tip AFM, decreases linearly with virus loading, from 270 μS/cm for pure PEDOT films to 50 μS/cm for films containing 100 μM virus. The presence on the virus surface of displayed affinity peptides did not significantly influence the efficiency of incorporation into virus-PEDOT biocomposite films.     

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     

UV cured transparent films including non‐aqueous conductive microgels

UV cured transparent films containing non‐aqueous conductive microgels coated with poly(aniline)/dodecyl benzenesulfonic acid(DBSA) were obtained. The conductive microgels were prepared by interface polymerization of aniline/DBSA in the presence of non‐aqueous polymeric microgels. The electrical conductivity and the particle size of the prepared conductive microgel were 0.5 S/cm and 58 nm, respectively. The prepared conductive microgels were easily blended with a UV curable coating formulation, and then were cured to make highly optically transparent films. For the UV cured film containing about 35 wt% of the conductive microgels, a surface resistance in the range of 10⁷ to 10⁸ Ω/square was obtained. In a polar cosolvent, such as NMP and m‐cresol, the critical volume was shifted to the lower range, with a value of 10 wt%. The UV cured films containing the conductive microgels exhibited good electrical stability against the thermal aging and humidity. Copyright © 2002 John Wiley & Sons, Ltd.     

自组装超薄膜修饰Ta2O5介质膜及其特性研究

采用静电自组装方法在五氧化二钽(Ta2O5)介质氧化膜上制备了聚二烯丙基二甲基氯化铵(PDDA)/聚苯乙烯磺酸钠(PSS)和聚二烯丙基二甲基氯化铵/聚-3,4-乙烯二氧噻吩-聚苯乙烯磺酸钠(PEDOT-PSS)超薄膜.研究了两种自组装超薄膜在Ta2O5介质氧化薄膜上的组装特性.结果表明两种自组装膜能够稳定地组装于Ta2O5介质膜表面,并有效降低薄膜的表面粗糙度.进一步研究了两种自组装超薄膜修饰的Ta2O5电容结构的电性能.结果表明静电自组装膜对Ta2O5介质膜表面进行修饰后,有效地隔离了介质氧化膜中的缺陷,降低了电容的漏电流并提高耐电压能力;研究还发现不同厚度的超薄膜对Ta2O5电容结构的耐压特性有不同程度的影响,较厚的薄膜可以更好地提高电容的耐压能力并降低漏电流,但会增加电容的等效串联电阻(ESR).另外,在相同薄膜层数的情况下,聚合物电解质PEDOT-PSS良好的导电性能降低了复合超薄膜的电阻,使得PDDA/PEDOT-PSS修饰的电容结构ESR值较低.     

Sb掺杂纳米TiO2光催化剂的晶体结构与光催化性能

Nanoscale Sb doped titanium dioxide thin films photocatalyst (Ti1-xSbO2) were obtained from dip-coating sol-gel method. The influence of dopant Sb density on the crystal structure and the phase transformation of the thin films were characterized by X-ray diffraction (XRD) and Raman spectra. The results of XRD showed that as-prepared films were not only in anatase state but also in brookite. The crystalline size was estimated to be around 13.3-20 nm. Raman spectra indicated there coexisted other phases and a transformation from brookite to anatase in the samples doped with 0.2% Sb. After doping a proper amount of Sb, the crystallization rate and the content of the anatase Ti1?xSbO2 in the thin films was clearly enhanced because Sb replaced part of the Ti of TiO2 in the thin films. The anode current density (photocurrent density) and the first order reaction speed constant (k) of thin films doped with 0.2% Sb reached 42.49 1A/cm2 and 0.171 h/cm2 under 254 nm UV illumination, respectively, which is about 11 times and 2 times that of the non-doped TiO2 anode prepared by the same method respectively.     

Study on the Structure and Properties of Ordered Conductive Polymer Ultrathin Film

A Langmuir-Blodgett (LB) inducing method was firstly used to prepare single layer and multilayer conducting composite PEDOT-PSS film. The film-forming ability of ionization ODA and ODA-SA monolayer spread on PEDOT-PSS nanoparticle sub-phase and the behavior of ODA/PEDOT-PSS assembly particles on pure water were firstly investigated. The results indicated that nanoparticles in the suphase are packed in the ionization monolayer and stable complex Langmuir film is formed at the air/water interface. It has been found that the best film-forming conditions for composite film are as follows:distinct interface was formed between ODA and PEDOT-PSS layer and single layer thickness of PEDOT-PSS was about 23 nm,well accordant to the size of PEDOT-PSS nanoparticles. Different structures were designed to test the conductive ability of these composite films and a variable range hopping (VRH) model was used to explain the film conductive mechanism. The results indicated that a 3D-VRH model explained well the transferring of charge carrier in the multilayer film.     

Influence of a water rinse on the structure and properties of poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) films

Poly(3,4-ethylene dioxythiophene):poly(styrene sulfonic acid) (PEDOT:PSS) films exhibit a complex structure of interconnected conductive PEDOT domains in an insulating PSS matrix that controls their electrical properties. This structure is modified by a water rinse, which removes PSS with negligible PEDOT loss. Upon PSS removal, film thickness is reduced by 35%, conductivity is increased by 50%, and a prominent dielectric relaxation is eliminated. These results suggest that the removed PSS is not associated with PEDOT and that the conductive domain network is not substantially altered by the removal of a significant fraction of insulator. The removal of PSS may benefit organic light emitting diode fabrication by reducing acid attack on indium tin oxide electrodes and lead to more robust performance in switching circuits by extending the working frequency range.