Synthesis, characterization, and electrical properties of regioregular alkyl-substituted PEDOTt

The regioregular hexyl-substituted poly(3,4-ethylenedioxy-2-thiophenylthiophene) (PEDOTt), structurally alternating copolymer of EDOT and thiophene, was synthesized via the Grignard Metathesis (GRIM) using catalytic amounts of Ni(dppp)Cl2. The products were characterized by 1H NMR spectroscopy, UV-vis spectroscopy and XRD. The alkyl-substituted conjugated polymer showed an enhancement of solubility in common organic solvents. Based on XRD data, the regioregular hexyl-substituted poly(3,4-ethylenedioxy-2-thiophenylthiophene) (PEDOTt) shows better crystallinity than the regiorandom hexyl-substituted PEDOTt owing to self-ordering. In addition, regioregular hexyl-PEDOTt has a conductivity of 0.788 S/cm by iodine doping.     

Hybrid organic on inorganic semiconductor heterojunction

Hybrid organic on inorganic semiconductor heterojunctions with a sandwich structure have been fabricated and studied using conjugated polymers. The inorganic semiconductor was n-type silicon substrate. The conjugated polymers used include poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) containing polyhedral oligomeric silsesquioxanes (MEH-PPV POSS), regioregular poly(3-hexylthiophene) (RR-P3HT) and poly(3,4-ethylenedioxythiophene) (PEDOT). Current density–voltage and capacitance–voltage measurements were performed. All of the devices displayed a rectifying characteristic. Among these devices, the first ever reported PEDOT doped with BF₃ on n-Si heterojunction devices showed the best performance with a rectification ratio around 5.7 × 10⁵ at ± 2 V and an ideality factor of 2.3. The results showed better device performance with decreased potential barrier height at the organic–inorganic interface. Results also suggested that smaller energy level offset between the HOMO of the conjugated polymer and the work function of anode metal will improve device performance.     

Volatile organic compound detection using nanostructured copolymers

Regioregular polythiophene-based conductive copolymers with highly crystalline nanostructures are shown to hold considerable promise as the active layer in volatile organic compound (VOC) chemresistor sensors. While the regioregular polythiophene polymer chain provides a charge conduction path, its chemical sensing selectivity and sensitivity can be altered either by incorporating a second polymer to form a block copolymer or by making a random copolymer of polythiophene with different alkyl side chains. The copolymers were exposed to a variety of VOC vapors, and the electrical conductivity of these copolymers increased or decreased depending upon the polymer composition and the specific analytes. Measurements were made at room temperature, and the responses were found to be fast and appeared to be completely reversible. Using various copolymers of polythiophene in a sensor array can provide much better discrimination to various analytes than existing solid state sensors. Our data strongly indicate that several sensing mechanisms are at play simultaneously, and we briefly discuss some of them.     

Revealing the Enhanced Thermoelectric Properties of Controllably Doped Donor-Acceptor Copolymer: The Impact of Regioregularity

Albeit considerable attention to the fast-developing organic thermoelectric (OTE) materials due to their flexibility and non-toxic features, it is still challenging to design an OTE polymer with superior thermoelectric properties. In this work, two “isomorphic” donor–acceptor (D–A) conjugated polymers are studied as the semiconductor in OTE devices, revealing for the first time the internal mechanism of regioregularity on thermoelectric performances in D–A type polymers. A higher molecular structure regularity can lead to higher crystalline order and mobility, higher doping efficiency, order of energy state, and thermoelectric (TE) performance. As a result, the regioregular P2F exhibits a maximum power factor (PF) of up to 113.27 µW m⁻¹ K⁻², more than three times that of the regiorandom PRF (35.35 µW m⁻¹ K⁻²). However, the regular backbone also implies lower miscibility with a dopant, negatively affecting TE performance. Therefore, the trade-off between doping efficiency and miscibility plays a vital role in OTE materials, and this work sheds light on the molecular design strategy of OTE polymers with state-of-the-art performances.     

Chemical vapor phase polymerization deposition of layer-ordered conducting polymer nanostructure for hole injection layer

Layer-ordered and ultrathin films of conducting polymer poly(3,4-ethylene dioxythiophene) (PEDOT) was prepared through a chemical vapor phase polymerization method. The chemical polymerization of 3, 4-ethylenedioxythiophene monomer was initiated in as-prepared oxidant LB films,and PEDOT nanofilms with layer-ordered structure was constructed. UV-Vis absorption spectrum and Fourier transform infrared spectroscopy was used to confirm an interface polymerization of PEDOT in as-prepared LB films. The results of X-ray diffraction and secondary ion mass spectrometry revealed that conductive PEDOT ultrathin layers were well located at different planes of LB films. The film deposition surface pressure and chemical polymerization time of PEDOT monomer in as-prepared LB films showed distinct influence on surface morphology and conductive performance of the polymerized PEDOT LB films. This layer-ordered conducting polymer ultrathin films was deposited on ITO surface as hole injection layer for organic light-emitting diodes, and the luminescence performance of devices was improved as well.     

Significant vertical phase separation in solvent-vapor-annealed poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) composite films leading to better conductivity and work function for high-performance indium tin oxide-free optoelectronics

In the present study, a novel polar-solvent vapor annealing (PSVA) was used to induce a significant structural rearrangement in poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) films in order to improve their electrical conductivity and work function. The effects of polar-solvent vapor annealing on PEDOT:PSS were systematically compared with those of a conventional solvent additive method (SAM) and investigated in detail by analyzing the changes in conductivity, morphology, top and bottom surface composition, conformational PEDOT chains, and work function. The results confirmed that PSVA induces significant phase separation between excess PSS and PEDOT chains and a spontaneous formation of a highly enriched PSS layer on the top surface of the PEDOT:PSS polymer blend, which in turn leads to better 3-dimensional connections between the conducting PEDOT chains and higher work function. The resultant PSVA-treated PEDOT:PSS anode films exhibited a significantly enhanced conductivity of up to 1057 S cm(-1) and a tunable high work function of up to 5.35 eV. The PSVA-treated PEDOT:PSS films were employed as transparent anodes in polymer light-emitting diodes (PLEDs) and polymer solar cells (PSCs). The cell performances of organic optoelectronic devices with the PSVA-treated PEDOT:PSS anodes were further improved due to the significant vertical phase separation and the self-organized PSS top surface in PSVA-treated PEDOT:PSS films, which can increase the anode conductivity and work function and allow the direct formation of a functional buffer layer between the active layer and the polymeric electrode. The results of the present study will allow better use and understanding of polymeric-blend materials and will further advance the realization of high-performance indium tin oxide (ITO)-free organic electronics.     

Near-ohmic behavior for conducting polymers: extension beyond PEDOT on gold-plated platinum to other polymer-counterion/substrate combinations

Conducting polymers constitute a class of materials for which electrochemical and electron transport properties are a function not only of their chemical identity but also of their complex morphology. In this paper, we investigate and compare the frequency dependence behavior of the impedance of poly(3,4-ethylenedioxythiophene), or PEDOT, and that of poly(3,4-ethylenedioxypyrrole), or PEDOP, which are doped with a series of polyatomic anions during electrodeposition. We also contrast the behavior of PEDOT on Pt|Au, Pt, glassy carbon, and gold. Initial results for polycarbazole, PCz, electrodes are, in addition, included. Deposition parameters were adjusted to produce morphologically similar films for PEDOT, PEDOP, and PCz. In doing so, we have been successful in producing frequency-independent impedance behavior similar to that previously reported for PEDOT on Pt|Au. Although the impedance behavior of these polymers appears to be primarily determined by morphological features, the impact of counterion identity (beyond ionic charge transport) is also discussed. These studies suggest that choice of polymer/dopant combination and electrodeposition parameters can be manipulated to tune the impedance characteristics of electrodes, thereby optimizing them for capacitive or faradaic charge injection, or some combination of the two.     

Facile route to prepare film of poly(3,4-ethylene dioxythiophene)-TiO2 nanohybrid for solar cell application

Composite using poly(3,4-ethylenedioxythiophene) (PEDOT) as electronic conducting polymer and nanocrystalline titanium dioxide (TiO₂) as host matrix were prepared by the template method. We applied an original in situ photopolymerization technique to synthesize PEDOT inside the TiO₂ pore and characterized the polymer and pore filling by different analysis (cyclic voltammetry, atomic force microscopy, spectroscopy and thermogravimetric measurements). Results were compared with those obtained on PEDOT films synthezised by monomer oxidization in the presence of FeCl₃. In situ generation of PEDOT by photopolymerization was observed to be higher and self-limiting after 22% filling of the mesoporous TiO₂ network. Hybrid materials were used to fabricate an indium-tin oxide/nano-crystalline TiO₂/PEDOT/Au device. The current-voltage characteristics indicate that a built-in electrical field has been created at the nano-crystalline TiO₂/PEDOT interface with energy conversion efficiency of 0.09% without dye.     

Conducting‐Polymer Nanotubes Improve Electrical Properties,Mechanical Adhesion,Neural Attachment,and Neurite Outgrowth of Neural Electrodes

An in vitro comparison of conducting‐polymer nanotubes of poly(3,4‐ethylenedioxythiophene) (PEDOT) and poly(pyrrole) (PPy) and to their film counterparts is reported. Impedance, charge‐capacity density (CCD), tendency towards delamination, and neurite outgrowth are compared. For the same deposition charge density, PPy films and nanotubes grow relatively faster vertically, while PEDOT films and nanotubes grow more laterally. For the same deposition charge density (1.44 C cm^?2), PPy nanotubes and PEDOT nanotubes have lower impedance (19.5 ± 2.1 kΩ for PPy nanotubes and 2.5 ± 1.4 kΩ for PEDOT nanotubes at 1 kHz) and higher CCD (184 ± 5.3 mC cm^?2 for PPy nanotubes and 392 ± 6.2 mC cm^?2 for PEDOT nanotubes) compared to their film counterparts. However, PEDOT nanotubes decrease the impedance of neural‐electrode sites by about two orders of magnitude (bare iridium 468.8 ± 13.3 kΩ at 1 kHz) and increase capacity of charge density by about three orders of magnitude (bare iridium 0.1 ± 0.5 mC cm^?2). During cyclic voltammetry measurements, both PPy and PEDOT nanotubes remain adherent on the surface of the silicon dioxide while PPy and PEDOT films delaminate. In experiments of primary neurons with conducting‐polymer nanotubes, cultured dorsal root ganglion explants remain more intact and exhibit longer neurites (1400 ± 95 µm for PPy nanotubes and 2100 ± 150 µm for PEDOT nanotubes) than their film counterparts. These findings suggest that conducting‐polymer nanotubes may improve the long‐term function of neural microelectrodes.     

Controlled doping of double walled carbon nanotubes and conducting polymers in a composite: An in situ Raman spectroelectrochemical study

The interaction of double wall carbon nanotubes (DWCNTs) and the conducting polymer poly(3,4-ethylenedioxythiphene)/polystyrenesulfonate (PEDOT/PSS) was studied by in-situ Raman spectroelectrochemistry. The mixing of DWCNTs with PEDOT/PSS caused a partial doping of the outer tube of DWCNTs, which was indicated by the relative change of the Raman intensity of the DWCNTs features. On the other hand, the bands corresponding to inner tubes of DWCNTs and to the polymer were almost untouched by assembling both species into a composite. The in-situ Raman spectroelectrochemical experiments have shown that the changes in electronic structure of inner tubes of DWCNTs embedded in PEDOT/PSS matrix are dependent on the doping level. While at the low doping level of the composite, the Raman features of inner tubes of DWCNTs do not change significantly, at high doping level they reflect the changes caused by the applied electrochemical potential similar to those observed in the polymer-free DWCNTs.     

Electrochemical performance of conducting polymer and its nanocomposites prepared by chemical vapor phase polymerization method

In this work, conducting polymers poly(3,4-ethylenedioxythiophene) (PEDOT), PEDOT/carbon nanotubes (CNTs), and PEDOT/reduced graphene oxide (RGO) were prepared via an in situ chemical vapor phase polymerization (VPP) process. Experiment results showed that PEDOT and PEDOT nanocomposites were uniformly constructed in oxidant and oxidant nanocomposite films through a modifying template effect. The VPP PEDOT and its nanocomposites were built on aluminium film as supercapaitor electrode materials and electrochemical capacitive properties were investigated by using cycle voltammetry and charge/discharge techniques. The VPP PEDOT exhibited a specific capacitance of 92 F/g at a current density of 0.2 A/g. The VPP PEDOT composites consisting of CNTs and RGO displayed specific capacitances of 137 and 156 F/g, respectively, at the same current density. For VPP nanocomposites, more than 80 % of initial capacitance was retained after 1,000 charge/discharge cycles, suggesting a good cycling stability for electrochemical electrode materials. The good capacitive performance of the conducting polymer nanocomposites are contributed to the synergic effect of the two components.     

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.     

改善有机片式固体钽电解电容器性能工艺研究

研究了在被膜过程中表面活性处理及掺杂对聚合物片式钽电容器容量、耐压、等效串联电阻(ESR)等特性的影响。研究结果表明表面活性处理后可以有效改善Ta2O5/PEDOT界面间的匹配,提高电容器容量引出效率;通过添加中间阻隔层(硅烷偶联剂)可以有效地阻挡杂质氧化性离子进入介质膜Ta2O5层,降低聚合物片式钽电容器的漏电流,提高耐压特性;实验结果表明在掺杂剂溶液的浓度为3%,补形成电压为赋能电压的70%时,能有效降低电容器ESR及漏电流。     

反向胶束法制备PEDOT纳米粒子气体敏感性的研究

通过用紫外-可见-近红外光谱、X射线光电子能谱及透射电镜等手段对采用反向胶束合成法,以二乙基磺基琥珀酸钠(AOT)形成的反胶束为模板制备出的导电聚合物聚3,4乙烯二氧噻吩(PEDOT)纳米粒子对HCl气体敏感性进行研究。沉积有纳米粒子的QCM器件对2.0×10-5气体响应时间为20s,具有较好的响应恢复特性,能够有效探测低浓度(5×10-6)气体,气敏特性明显优于普通PEDOT粒子。     

Electrochemical co-deposition of bimetallic Pt-Ru nanoclusters dispersed on poly(3,4-ethylenedioxythiophene) and electrocatalytic behavior for methanol oxidation

Nanoclusters of bimetallic Pt-Ru are electrochemically deposited on conductive polymer, poly(3,4-ethylenedioxythiophene) (PEDOT), which is also electrochemically deposited on a carbon paper substrate. The bimetallic deposition is carried out in an acidic electrolyte consisting of chloroplatinic acid and ruthenium chloride at 0.0 V versus saturated calomel electrode (SCE) on PEDOT coated carbon paper. A thin layer PEDOT on a carbon paper substrate facilitates the formation of uniform, well-dispersed, nano clusters of Pt-Ru of mean diameter of 123 nm, which consist of nanosize particles. In the absence of PEDOT, the size of the clusters is about 251 nm, which are unevenly distributed on carbon paper substrate. Cyclic voltammetry studies suggest that peak currents of methanol oxidation are several times greater on PtRu-PEDOT electrode than on Pt-Ru electrode in the absence of PEDOT.     

Conducting polymer and reduced graphene oxide Langmuir–Blodgett films: a hybrid nanostructure for high performance electrode applications

In this work, we prepared a reduced graphene oxide (RGO)/poly(3,4-ethylenedioxythiophene) (PEDOT) hybrid composite with well defined nanostructure. The graphene oxide (GO) was first deposited on substrate through the Langmuir–Blodgett (LB) deposition, which provided a tunable and ordered GO arrangement on substrate. Then the GO LB films were reduced to RGO by following thermal treatment, and a ultrathin conducting polymer (CP) PEDOT was directly coated on RGO through a vapor phase polymerization process. The RGO/PEDOT nanocomposite exhibits excellent electrical conductivity about 377.2 S/cm. Electrochemical activity investigation revealed that this nanocomposite exhibits 213 F/g high specific capacitance at a 0.5 A/g current density and shows better capacitance retention rate than pure PEDOT. The detailed study also confirmed that the arrangement of RGO shows distinct influence on the electrical and electrochemical properties of obtained nanocomposite. Large area RGO/PEDOT nanocomposite with high conductivity and electrochemical activity can be deposited on different substrates. Such high conductivity and electrochemical activity RGO/CP nanocomposite shows promising application future in organic and flexible electrode materials for sustainable energy storage.     

Nonvolatile write-once-read-many-times memory device with functionalized-nanoshells/PEDOT:PSS nanocomposites

We have investigated the memory effect of the nanocomposites of functionalized carbon nanoshells (f-CNSs) mixed with poly(3,4-ethylenedioxythiophene) doped with polystyrenesulfonate (PEDOT:PSS) polymer. The f-CNSs were synthesized by the spray pyrolysis method and functionalized in situ with functional groups (OH, COOH, C-H, C-OH) with the aim of improving their compatibility in the aqueous dispersion of PEDOT:PSS. The current-voltage (I-V) sweep curves at room temperature for the Al/f-CNSs, for certain concentrations range, embedded in a PEDOT:PSS layer/Al devices showed electrical bistability for write-once-read-many-times (WORM) memory devices. The memory effect observed in the devices can be explained due to the existence of trapped charges in the f-CNSs/PEDOT:PSS layer. The carrier transport mechanisms for the memory devices is studied and discussed.     

Polymeric memory elements and logic circuits that store multiple bit states

The ever-increasing flow of information requires new approaches for high-density data storage (HDDS). Here, we present a novel solution that incorporates the easily accessible polymer poly(3,4-ethylenedioxythiophene) (PEDOT) with multistate memory. The electrical addressable polymer is able to store up to five different memory states, which are stable up to 20 min. The observed memory states are generated by the optical output signature of the PEDOT deposited on indium tin oxide (ITO) coated glass, upon applying specific electrical inputs. Moreover, the demonstrated platforms can be represented by a general logic circuit, which allows the construction of multistate memory, such as flip-flops and flip-flap-flop logic circuits.     

Laser-induced forward transfer of polymer light-emitting diode pixels with increased charge injection

Laser-induced forward transfer (LIFT) has been used to print 0.6 mm × 0.5 mm polymer light-emitting diode (PLED) pixels with poly[2-methoxy, 5-(2-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) as the light-emitting polymer. The donor substrate used in the LIFT process is covered by a sacrificial triazene polymer (TP) release layer on top of which the aluminium cathode and functional MEH-PPV layers are deposited. To enhance electron injection into the MEH-PPV layer, a thin poly(ethylene oxide) (PEO) layer on the Al cathode or a blend of MEH-PPV and PEO was used. These donor substrates have been transferred onto both plain indium tin oxide (ITO) and bilayer ITO/PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) blend) receiver substrates to create the PLED pixels. For comparison, devices were fabricated in a conventional manner on ITO substrates coated with a PEDOT:PSS hole-transporting layer. Compared to multilayer devices without PEO, devices with ITO/PEDOT:PSS/MEH-PPV:PEO blend/Al architecture show a 100 fold increase of luminous efficiency (LE) reaching a maximum of 0.45 cd/A for the blend at a brightness of 400 cd/m(2). A similar increase is obtained for the polymer light-emitting diode (PLED) pixels deposited by the LIFT process, although the maximum luminous efficiency only reaches 0.05 cd/A for MEH-PPV:PEO blend, which we have attributed to the fact that LIFT transfer was carried out in an ambient atmosphere. For all devices, we confirm a strong increase in device performance and stability when using a PEDOT:PSS film on the ITO anode. For PLEDs produced by LIFT, we show that a 25 nm thick PEDOT:PSS layer on the ITO receiver substrate considerably reduces the laser fluence required for pixel transfer from 250 mJ/cm(2) without the layer to only 80 mJ/cm(2) with the layer.     

Influence of Biodopants on PEDOT Biomaterial Polymers: Using QCM‐D to Characterize Polymer Interactions with Proteins and Living Cells

Organic conducting polymers (OCPs) are currently the subject of intense research in the area of biomaterials and bioelectronics. Of the OCPs, poly(3,4‐ethylenedioxythiophene) (PEDOT) has attracted significant interest, however there has been little work on investigating the incorporation of biological compounds as the dopant species in the polymer which are aimed at enhancing the biocompatibility and biofunctionality of the material. Here, we incorporate the biological dopants dextran sulphate, chondroitin sulphate, and alginate, into PEDOT polymers and investigate their influence on a suite of physicochemical and electrochemical properties. We employ QCM‐D to study the mass of adsorption and the viscoelastic properties of the important extracellular matrix proteins fibronectin and collagen. Furthermore, we use QCM‐D to study the adhesion of PC12 neural cells to the PEDOT‐biodopant polymers with and without an adsorbed protein conditioning layer. QCM‐D was found to be an excellent tool with which to study conducting polymer–biological interactions, with this report the first time that QCM‐D has been used to study cell interactions with conducting polymer biomaterials.