Effects of Secondary Dopant Anions on Emissivity and Related Properties of Poly(3,4-ethylenedioxythiophene).

Smart materials that are energy efficient and take up less space are crucial in the development of new technologies. Electrochromic polymers (ECPs) are one such class of materials that actively change their optical behavior in both visible and infrared parts of the electromagnetic spectrum. They show promise in a wide range of applications, from active camouflage to smart displays/windows. The full capabilities of ECPs are still yet to be explored, for while their electrochromic properties are well established, their Infrared (IR) modulation is less reported on. This study addresses the potential of ECPs in active IR modulating devices by optimization of Vapor Phase Polymerized poly(3,4-ethylenedioxythiophene) (PEDOT) thin films via the substitution of its dopant anion. Dynamic ranges denoting emissivity changes between reduced and oxidized states of PEDOT are found across dopants of tosylate, bromide, sulfate, chloride, perchlorate, and nitrate. Relative to the emissivity of reduced (neutral) PEDOT, a range of ±15% is achieved from the doped PEDOT films, and a maximum dynamic range of 0.11 across a 34% change is recorded for PEDOT doped with perchlorate.

Hydrolysis of doped conducting polymers.

Conducting polymers display a range of interesting properties, from electrical conduction to tunable optical absorption and mechanical flexibility, to name but a few. Their properties arise from positive charges (carbocations) on their conjugated backbone that are stabilised by counterions doped in the polymer matrix. In this research we report hydrolysis of these carbocations when poly(3,4-ethylenedioxy thiophene) is exposed to 1 mM aqueous salt solutions. Remarkably, two classes of anion interactions are revealed; anions that oxidise PEDOT via a doping process, and those that facilitate the SN1 hydrolysis of the carbocation to create hydroxylated PEDOT. A pKa of 6.4 for the conjugate acid of the anion approximately marks the transition between chemical oxidation and hydrolysis. PEDOT can be cycled between hydrolysis and oxidation by alternating exposure to different salt solutions. This has ramifications for using doped conducting polymers in aqueous environments (such as sensing, energy storage and biomedical devices).

Influence of PEG-ran-PPG Surfactant on Vapour Phase Polymerised PEDOT Thin Films.

The oxidant, Fe(III) tosylate, was used in the vapour phase polymerisation (VPP) of PEDOT. The amphiphilic co-polymer poly(ethylene glycol-ran-propylene glycol) was added and its influence examined. Both the PEDOT conductivity and optical contrast range increased with the inclusion of the co-polymer, with the maximum being recorded at 4 wt.-%. Loadings higher than this resulted in a systematic decrease in both conductivity and optical contrast. Evidence indicates that in addition to the beneficial anti-crystallisation effect to the oxidant layer, the co-polymer also reduces the effective reactivity of the oxidant, as demonstrated by slower polymerisation rates. Confirmation of the change in polymerisation rate was obtained using a quartz crystal microbalance (QCM). The slower polymerisation rate results in higher conductivity and optical contrast; however, XPS data confirmed that the co-polymer remained within the PEDOT film post-washing and this result explains why the performance decreases at high surfactant loadings.

Structural Control of Charge Storage Capacity to Achieve 100% Doping in Vapor Phase-Polymerized PEDOT/Tosylate.

Vapor phase polymerization (VPP) is used to fabricate a series of tosylate-doped poly(3,4-ethylenedioxythiophene) (PEDOT) electrodes on carbon paper. The series of VPP PEDOT/tosylate coatings has varying levels of crystallinity and electrical conductivity because of the use (or not) of nonionic triblock copolymers in the oxidant solution during synthesis. As a result, the impact of the structure on charge storage capacity is investigated using tetra-n-butylammonium hexafluorophosphate (0.1 M in acetonitrile). The ability to insert anions, and hence store charge, of the VPP PEDOT/tosylate is inversely related to its electrical conductivity. In the case of no nonionic triblock copolymer employed, the VPP PEDOT/tosylate achieves electrochemical doping levels of 1.0 charge per monomer or greater (≥100% doping level). Such high doping levels are demonstrated to be plausible by molecular dynamics simulations and density functional theory calculations. Experiments show that this high doping level is attainable when the PEDOT structure is weakly crystalline with (relatively) large crystallite domains.

Influence of Postsynthesis Heat Treatment on Vapor-Phase-Polymerized Conductive Polymers.

The effect of thermal treatment on the structure and electrical/optical properties of vapor phase-polymerized poly(3,4-ethylenedioxythiophene):tosylate (PEDOT:Tos) and polypyrrole:tosylate (PPy:Tos) polymer films was investigated. Thermal treatment was applied postpolymerization but prior to washing the embedded oxidant layer out of the polymer film. Structural and chemical changes arising from the treatment were studied in the context of their conductive and electrochromic behavior. Spectroscopic analysis indicated a rise in the doping levels of both conductive polymers when exposed to thermal treatment. Additionally, an increase in the film thickness was recorded after the oxidant and other unbound species were removed from the polymer layer using an ethanol rinse. As such, a strong indication that polymerization continued even in the absence of (external) monomer vapor was present. This film thickness increase was most pronounced for PPy:Tos but also present in the PEDOT:Tos film. Heat-treated films exhibited enhanced cohesion, making them more robust and therefore increasing the viability for the material to be used in the optoelectronics area. This robustness, due to additional (cross-linking) oligomer growth, came at the expense of lower conductivity relative to their untreated counterparts.

Nanoporous glass films on liquids.

Glass-like thin films are used in many applications as dielectric layers, barrier coatings, abrasion-resistant films, and/or transparent films. We report the first direct application of such materials to liquid substrates using a plasma-deposition process at atmospheric pressure. The study demonstrates the broader utilization of these materials, for example, as robust membranes for water harvesting or drug delivery.

Large area nanostructured arrays: optical properties of metallic nanotubes.

In this study, large area metallic nanotube arrays on flexible plastic substrates are produced by templating the growth of a cosputtered alloy using anodized aluminum oxide membranes. These nanotube arrays are prepared over large areas (ca. squared centimeters) by reducing the residual stress within the thin multilayered structure. The nanotubes are approximately 20 nm in inner diameter, having walls of <10 nm in thickness, and are arranged in a close packed configuration. Optically the nanotube arrays exhibit light trapping behavior (not plasmonic), where the reflectivity is less than 15% across the visible spectra compared to >40% for a flat sample using the same alloy. When the nanotubes are exposed to high relative humidity, they spontaneously fill, with a concomitant change in their visual appearance. The filling of the nanotubes is confirmed using contact angle measurements, with the nanotubes displaying a strong hydrophilic character compared to the weak behavior of the flat sample. The ability to easily fabricate large area nanotube arrays which display exotic behavior paves the way for their uptake in real world applications such as sensors and solar energy devices.