Tuning Thermal Transport in Chain‐Oriented Conducting Polymers for Enhanced Thermoelectric Efficiency: A Computational Study

Thermoelectric polymers should be electron‐crystal and phonon‐glass to efficiently interconvert heat and electricity. Herein, by using molecular dynamics simulations, it is demonstrated that engineering phonon transport in conducting polymers by tailoring its degree of polymerization can effectively improve the energy conversion efficiency. This is based on the separated length scales that charge carriers and phonons travel along the polymer backbone. By tuning the chain length and the crystallinity of chain‐oriented poly(3,4‐ethylenedioxythiophene) fibers, a dramatic decrease of the axial thermal conductivity to 0.97 W m^?1 K^?1 has been observed in rationally designed polymer fibers with the crystallinity of 0.49 and the relative molecular weight of 5600. The dimensionless thermoelectric figure of merit at 298 K has been enhanced to 0.48, which is approximately one order of magnitude higher than that in crystalline polymers.     

Patterning and Conductivity Modulation of Conductive Polymers by UV Light Exposure

A novel patterning technique of conductive polymers produced by vapor phase polymerization is demonstrated. The method involves exposing an oxidant film to UV light which changes the local chemical environment of the oxidant and subsequently the polymerization kinetics. This procedure is used to control the conductivity in the conjugated polymer poly(3,4‐ethylenedioxythiophene):tosylate by more than six orders of magnitude in addition to producing high‐resolution patterns and optical gradients. The mechanism behind the modulation in the polymerization kinetics by UV light irradiation as well as the properties of the resulting polymer are investigated.     

Screen‐Printed Poly(3,4‐Ethylenedioxythiophene):Poly(Styrenesulfonate) Grids as ITO‐Free Anodes for Flexible Organic Light‐Emitting Diodes

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT: PSS) grids have been successfully constructed by roll‐to‐roll compatible screen‐printing techniques and have been used as indium tin oxide (ITO)‐free anodes for flexible organic light‐emitting diodes (OLEDs). The grid‐type transparent conductive electrodes (TCEs) can adopt thicker PEDOT: PSS grid lines to ensure the conductivity, while the mesh‐like grid structure can play an important role to maintain high optical transparency. By adjusting grid periods, grid thickness and treatment of organic additives, PEDOT: PSS TCEs with high optical transparency, low sheet resistance, and excellent mechanical flexibility have been achieved. Using the screen‐printed PEDOT: PSS grids as the anodes, ITO‐free OLEDs achieved peak current efficiency of 3.40 cd A^?1 at the current density of 10 mA cm^?2, which are 1.56 times better than the devices with ITO glass as the anodes. The improved efficiency is attributed to the light extraction effect and improved transparency by the grid structure. The superior optoelectronic performances of OLEDs based on flexible screen‐printed PEDOT: PSS grid anodes suggest their great prospects as ITO‐free anodes for flexible and wearable electronic applications.     

Chemically Resistant,Shapeable, and Conducting Metal‐Organic Gels and Aerogels Built from Dithiooxamidato Ligand

Metal‐organic gels (MOGs) appear as a blooming alternative to well‐known metal‐organic frameworks (MOFs). Porosity of MOGs has a microstructural origin and not strictly crystalline like in MOFs; therefore, gelation may provide porosity to any metal‐organic system, including those with interesting properties but without a porous crystalline structure. The easy and straightforward shaping of MOGs contrasts with the need of binders for MOFs. In this contribution, a series of MOGs based on the assembly of 1D‐coordination polymer nanofibers of formula [M(DTA)]_n (M^II: Ni, Cu, Pd; DTA: dithiooxamidato) are reported, in which properties such as porosity, chemical inertness, mechanical robustness, and stimuli‐responsive electrical conductivity are brought together. The strength of the M? S bond confers an unusual chemical resistance, withstanding exposure to acids, alkalis, and mild oxidizing/reducing chemicals. Supercritical drying of MOGs provides ultralight metal‐organic aerogels (MOAs) with densities as low as 0.03 g cm^?3 and plastic/brittle behavior depending on the nanofiber aspect ratio. Conductivity measurements reveal a semiconducting behavior (10^?12 to 10^?7 S cm^?1 at 298 K) that can be improved by doping (10^?5 S cm^?1). Moreover, it must be stressed that conductivity of MOAs reversibly increases (up to 10^?5 S cm^?1) under the presence of acetic acid.     

Formation of Nanoislands on Conducting Poly(3,4‐ethylenedioxythiophene) Films by High‐Energy‐Ion Irradiation: Applications as Field Emitters and Capacitor Electrodes

Nanoislands have been fabricated on the surface of conducting poly(3,4‐ethylenedioxythiophene) (PEDOT) films doped with poly(4‐styrenesulfonate) (PSS) using high‐energy (≈ 1–3 MeV) Cl²⁺ ion irradiation. Scanning electron microscopy and atomic force microscopy confirm the direct formation of nanoislands with diameters ranging from 50 to 300 nm and heights ranging from 40 to 120 nm. From our analysis, we propose that the formation of nanoislands might be due to micelle formation of the polymeric stabilizer poly(sodium 4‐styrenesulfonate) (PSS‐Na) surrounding the nuclei in the PEDOT/PSS via the high‐energy‐ion irradiation. We observe similar results for high‐energy‐ion irradiated polyaniline doped with PSS‐Na. On using the nanoislands as nanotip emitters of a field‐emission display, an increase in the current density of about five orders of magnitude is observed. Cyclic voltammetry of the PEDOT/PSS electrode with the nanoislands as the electrode shows enhanced capacitance compared with that of the PEDOT/PSS film that contains no nanostructure.     

Electrochromic Window Based on Conducting Poly(3,4‐ethylenedioxythiophene)–Poly(styrene sulfonate)

A short survey of technological aspects of electrochromism with various electroactive species is given. Different approaches with inorganic and organic materials have been pursued in the past. So far widespread usage of this technology for large area applications has not been achieved. Nevertheless one major technical product, self‐darkening rear‐view mirrors for cars, is already well established. This article reviews some research results on electroactive polythiophenes, especially poly(3,4‐alkylenedioxythiophenes). Some promising results with the commercially available electrically conducting polymer Baytron P (PEDT/PSS) are presented. It is demonstrated that an all solid‐state electrochromic multilayer assembly based on a polymeric electrochromic material might be close to technical realization. The coating of large area substrates with aqueous poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) dispersion can be a way to an economically viable product.     

A Highly Stable,New Electrochromic Polymer: Poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy) thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene)

A highly stable new electrochromic polymer, poly(1,4‐bis(2‐(3′,4′‐ethylenedioxy)thienyl)‐2‐methoxy‐5‐2″‐ethylhexyloxybenzene) (P(BEDOT‐MEHB)) was synthesized and its electrochemical and electrochromic properties are reported. P(BEDOT‐MEHB) showed a very well defined electrochemistry with a relatively low oxidation potential of the monomer at + 0.44 V versus Ag/Ag⁺, E_1/2 at – 0.35 V versus Ag/Ag⁺ and stability to long‐term switching up to 5000 cycles. A high level of stability to over‐oxidation has also been observed as this material shows limited degradation of its electroactivity at potentials 1.4 V above its half‐wave potential. Spectroelectrochemistry showed that the absorbance of the π–π* transition in the neutral state is blue‐shifted compared to PEDOT, displaying a maximum at 538 nm (onset at 640 nm), thus giving an almost colorless, highly transparent oxidized polymer with a bandgap of 1.95 eV. Different colors observed at different oxidation levels and strong absorption in the near‐IR make this polymer a good candidate for several applications.     

Plastic Electronic Devices Through Line Patterning of Conducting Polymers

A novel method for the preparation of transparent conducting‐polymer patterns on flexible substrates is presented. This method, line patterning, employs mostly standard office equipment, such as drawing software, a laser printer, and commercial overhead transparencies, together with a solution or dispersion of a conducting polymer. The preparation of a seven‐segment polymer‐dispersed liquid‐crystal display using electrodes of the conducting polymer poly(3,4‐ethylenedioxythiophene) doped with poly(4‐styrene sulfonate) (PEDOT/PSS) is described in detail. Furthermore, a method to fabricate an eleven‐key push‐button array for keypad applications is presented. Properties of the electrode films and patterns are discussed using microscopy images, atomic force microscopy, conductivity measurements, and tests of film stability.     

Multifunctional Graphene–PEDOT Microelectrodes for On‐Chip Manipulation of Human Mesenchymal Stem Cells

All‐solution‐processed multifunctional organic bioelectronics composed of reduced graphene oxide (rGO) and dexamethasone 21‐phosphate disodium salt (DEX)‐loaded poly(3,4‐ethylenedioxythiophene) (PEDOT) microelectrode arrays on indium tin oxide glass are reported. They can be used to manipulate the differentiation of human mesenchymal stem cells (hMSCs). In the devices, the rGO material functions as an adhesive coating to promote the adhesion and alignment of hMSC cells and to accelerate their osteogenic differentiation. The poly(L ‐lysine‐graft‐ethylene glycol) (PLL‐g‐PEG)‐coated PEDOT electrodes serve as electroactive drug‐releasing electrodes. In addition, the corresponding three‐zone parallel devices operate as efficient drug‐releasing components through spatial‐temporal control of the release of the drug DEX from the PEDOT matrix. Such devices can be used for long‐term cell culturing and controlled differentiation of hMSCs through electrical stimulation.     

Towards a Transparent,Highly Conductive Poly(3,4‐ethylenedioxythiophene)

A detailed investigation of the processing parameters influencing the oxidative polymerization of 3,4‐ethylenedioxythiophene (EDOT) and a methanol‐substituted derivative (EDOT–CH₂OH) was performed with the goal of maximizing the conductivity of the polymer. We show that the conductivity can be significantly enhanced by varying the monomer, oxidant (iron(III ) p‐toluenesulfonate (Fe(OTs)₃)), weak base (imidazole (Im)), solvent (various alcohols), and solution concentrations. The effect of each variable on the final materials properties is investigated, and the parameters have been optimized to achieve conductivities as high as 900 S cm^–1. Surface resistance below 150 Ω/□ for 80–90 nm thick films with visible‐spectrum transparency exceeding 80 % is achieved. The combination of these properties makes the films highly suitable for numerous device applications.     

PEDOT:PSS‐Assisted Exfoliation and Functionalization of 2D Nanosheets for High‐Performance Organic Solar Cells

Here, a facial and scalable method for efficient exfoliation of bulk transition metal dichalcogenides (TMD) and graphite in aqueous solution with poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) to prepare single‐ and few‐layer nanosheets is demonstrated. Importantly, these TMD nanosheets retain the single crystalline characteristic, which is essential for application in organic solar cells (OSCs). The hybrid PEDOT:PSS/WS₂ ink prepared by a simple centrifugation is directly integrated as a hole extraction layer for high‐performance OSCs. Compared with PEDOT:PSS, the PEDOT:PSS/WS₂‐based devices provide a remarkable power conversion efficiency due to the “island” morphology and benzoid–quinoid transition. This study not only demonstrates a novel method for preparing single‐ and few‐layer TMD and graphene nanosheets but also paves a way for their applications without further complicated processing.     

Organo‐metal Diodes Based on a Nanoparticulate Poly(3,4‐ethylenedioxythiophene) Composite

Diodes composed of a nanoparticulate composite of poly(3,4‐ethylenedioxythiophene) and a Cu–Cu²⁺ redox couple in a poly(ethylene oxide)–LiBF₄ polymer‐electrolyte matrix between Ag and Zr electrodes show rectifications in excess of 50 000 at applied fields of 4 V. These large changes are considered to arise from both rectification at the Zr/ZrO₂ composite interface and from the switching of the composite material between two conductivity states by the application of a low potential field. The preparation and electrochemical characterisation of these novel active devices are discussed.     

In‐Situ Compositional and Structural Analysis of Plastic Solar Cells

Bulk‐heterojunction photovoltaic cells consisting of a photoactive layer of poly[2‐methoxy‐5‐(3′,7′‐dimethyloctyloxy)‐1,4‐phenylenevinylene] (MDMO‐PPV) and a C₆₀ derivative, (1‐(3‐methoxycarbonyl)propyl‐1‐phenyl‐[6,6]‐methanofullerene), (PCBM), sandwiched between an indium tin oxide (ITO) anode covered with poly(ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), and an aluminum cathode have been analyzed using transmission electron microscopy (TEM) and cryogenic Rutherford backscattering spectrometry (RBS) to assess the structural and elemental composition of these devices. TEM of cross sections of fully processed photovoltaic cells, prepared using a focused ion beam, provide a clear view of the individual layers and their interfaces. RBS shows that during preparation diffusion of indium into the PEDOT:PSS occurs while the diffusion of aluminum into the polymer layers is negligible. An iodinated C₆₀ derivative (I‐PCBM) was used to determine the concentration profile of this derivative in the vertical direction of a 100 nm active layer.     

High‐Conductivity Poly(3,4‐ethylenedioxythiophene):Poly(styrene sulfonate) Film and Its Application in Polymer Optoelectronic Devices

The conductivity of a poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) film can be enhanced by more than two orders of magnitude by adding a compound with two or more polar groups, such as ethylene glycol, meso‐erythritol (1,2,3,4‐tetrahydroxybutane), or 2‐nitroenthanol, to an aqueous solution of PEDOT:PSS. The mechanism for this conductivity enhancement is studied, and a new mechanism proposed. Raman spectroscopy indicates an effect of the liquid additive on the chemical structure of the PEDOT chains, which suggests a conformational change of PEDOT chains in the film. Both coil and linear conformations or an expanded‐coil conformation of the PEDOT chains may be present in the untreated PEDOT:PSS film, and the linear or expanded‐coil conformations may become dominant in the treated PEDOT:PSS film. This conformational change results in the enhancement of charge‐carrier mobility in the film and leads to an enhanced conductivity. The high‐conductivity PEDOT:PSS film is ideal as an electrode for polymer optoelectronic devices. Polymer light‐emitting diodes and photovoltaic cells fabricated using such high‐conductivity PEDOT:PSS films as the anode exhibit a high performance, close to that obtained using indium tin oxide as the anode.     

Internal Field Screening in Polymer Light‐Emitting Diodes

We use electromodulation spectroscopy and modeling studies to probe the electric‐field distribution in polyfluorene‐based polymer light‐emitting diodes containing poly(3,4‐ethylenedioxythiophene) poly(styrene sulfonate). The bulk internal field is shown to be zero under ordinary operating conditions, with trapped electrons close to the anode fully screening the bulk semiconductor from the external field. The effect has far‐reaching implications for the understanding and optimization of organic devices.