Semi-metallic polymers.

Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly(3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics.

Cell Viability Assessment of PEDOT Conducting Polymer-Coated Microneedles for Skin Sampling.

Recently, transdermal monitoring and drug delivery have gained much interest, owing to the introduction of the minimally invasive microneedle (MN) device. The advancement of electroactive MNs electrically assisted in the capture of biomarkers or the triggering of drug release. Recent works have combined conducting polymers (CPs) onto MNs owing to the soft nature of the polymers and their tunable ionic and electronic conductivity. Though CPs are reported to work safely in the body, their biocompatibility in the skin has been insufficiently investigated. Furthermore, during electrical biasing of CPs, they undergo reduction or oxidation, which in practical terms leads to release/exchange of ions, which could pose biological risks. This work investigates the viability and proliferation of skin cells upon exposure to an electrochemically biased MN pair comprising two differently doped poly(3,4-ethylenedioxy-thiophene) (PEDOT) polymers that have been designed for skin sampling use. The impact of biasing on human keratinocytes and dermal fibroblasts was determined at different initial cell seeding densities and incubation periods. Indirect testing was employed, whereby the culture media was first exposed to PEDOTs prior to the addition of this extract to cells. In all conditions, both unbiased and biased PEDOT extracts showed no cytotoxicity, but the viability and proliferation of cells cultured at a low cell seeding density were lower than those of the control after 48 h of incubation.

PEDOT coated microneedles towards electrochemically assisted skin sampling.

Skin sampling is a diagnostic procedure based on the analysis of extracted skin tissues and/or the observation of biomarkers in bodily fluids. Sampling using microneedles (MNs) that minimize invasiveness is gaining attention over conventional biopsy/blood lancet. In this study, new MNs for electrochemically assisted skin sampling are reported, specifically tailored for combined skin tissue biopsy and interstitial fluid (ISF) extraction. To overcome risks associated with using metal MNs, a highly electroactive, mechanically flexible, and biocompatible organic conducting polymer (CP) coated onto plastic is chosen as an alternative. Two different variants of doped poly(3,4-ethylenedioxythiophene) are coated on polymethyl methacrylate and used in combination as a MN pair with subsequent testing via a variety of electrochemical techniques to (i) give real-time information of the MN penetration depth into the skin, and (ii) yield new information on various salts present in the ISF. The MN skin sampler shows the ability to extract ions from the hydrated excised skin as a step towards in vivo ISF extraction. The presence of ions was analyzed using X-ray photoelectron spectroscopy. This added chemical information in conjunction with the existing biomarker analysis increases opportunity for disease/condition detection. For example, in the case of psoriasis, information about salt in the skin is invaluable in combination with pathogenic gene expression for diagnosis.

Understanding PEDOT doped with tosylate.

Now in their 5th decade of research and development, conducting polymers represent an interesting class of materials to underpin new wearable or conformable electronic devices. Of particular interest over the years has been poly(3,4-ethylenedioxythiophene), commonly known as PEDOT, owing to its ease of fabrication and relative stability under typical ambient conditions. Understanding PEDOT from a variety of fundamental and applied perspectives is important for how it can be enhanced, modified, functionalised, and/or processed for use in commercial products. This feature article highlights the contribution of the research team at the University of South Australia led by Professor Evans, and their collaborators, putting their work into the broader context of conducting polymer research and application. This review focuses on the vapour synthesis of PEDOT doped with the tosylate anion, the benefits of controlling its morphology/structure during synthesis, and its application as an active material interacting with secondary anions in sensors, energy devices and drug delivery.

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.

The origin of surface stress induced by adsorption of iodine on gold.

The cantilever technique for the measurement of film stress on both macroscopic and microscopic cantilevers is validated, then applied to the experimental determination of film stress induced by the adsorption of a monolayer of iodine onto a gold substrate. A model is proposed that relates the change in the interatom potential upon chemisorption of iodine onto gold to the measured film stress. Excellent agreement is found with the experimentally determined value. This result gives insight into the origins of film stress that is observed in all thin film and coating applications.

Sensing cantilever beam bending by the optical lever technique and its application to surface stress.

Cantilever beams, both microscopic and macroscopic, are used as sensors in a great variety of applications. An optical lever system is commonly employed to determine the deflection and thereby the profile of the cantilever under load. The sensitivity of the optical lever must be calibrated, and this is usually achieved by application of a known load or deflection to the free end of the cantilever. When the sensing operation involves a different type of load or a combination of types of loadings, the calibration and the deflection values derived from it become invalid. Here we develop a master equation that permits the true deflection of the cantilever to be obtained simply from the measurement of the apparent deflection for uniformly distributed loadings and end-moment loadings. These loadings are relevant to the uniform adsorption or application of material to the cantilever or the application of a surface stress to the cantilever and should assist experimentalists using the optical lever, such as in the atomic force microscope, to measure cantilever deflections in a great variety of sensing applications. We then apply this treatment to the experimental evaluation of surface stress. Three forms of Stoney's equation that relate the apparent deflection to the surface stress, which is valid for both macroscopic and microscopic experiments, are derived. Analysis of the errors arising from incorrect modeling of the loading conditions of the cantilever currently applied in experiments is also presented. It is shown that the reported literature values for surface stress in microscopic experiments are typically 9% smaller than their true value. For macroscopic experiments, we demonstrate that the added mass of the film or coating generally dominates the measured deflection and must be accounted for accurately if surface stress measurements are to be made. Further, the reported measurements generally use a form of Stoney's equation that is in error, resulting in an overestimation of surface stress by a factor >5.

Acido-basic control of the thermoelectric properties of poly(3,4-ethylenedioxythiophene)tosylate (PEDOT-Tos) thin films.

PEDOT-Tos is one of the conducting polymers that displays the most promising thermoelectric properties. Until now, it has been utterly difficult to control all the synthesis parameters and the morphology governing the thermoelectric properties. To improve our understanding of this material, we study the variation in the thermoelectric properties by a simple acido-basic treatment. The emphasis of this study is to elucidate the chemical changes induced by acid (HCl) or base (NaOH) treatment in PEDOT-Tos thin films using various spectroscopic and structural techniques. We could identify changes in the nanoscale morphology due to anion exchange between tosylate and Cl- or OH-. But, we identified that changing the pH leads to a tuning of the oxidation level of the polymer, which can explain the changes in thermoelectric properties. Hence, a simple acid-base treatment allows finding the optimum for the power factor in PEDOT-Tos thin films.

Aqueous processing of graphene-polymer hybrid thin film nano-composites and gels.

Research into the structure, properties and applications of graphene has moved at a tremendous pace over the past few years. This review describes one aspect of this research, that of the incorporation of graphene particles with a range of polymers to create novel hybrid materials with increased functionality such as improved conductance, increased strength and introduced biocompatibility or cytotoxicity. This review focuses on dispersing graphene in polymer matrices, both insulating and conducting. Additionally, a brief discussion of carbon based platelet production methods is given in order to provide context on the subsequent use of this family of materials such as graphene, graphene oxide (GO) and reduced graphene oxide (rGO) incorporated into polymeric thin films.

Laser actuation of cantilevers for picometre amplitude dynamic force microscopy.

As nanoscale and molecular devices become reality, the ability to probe materials on these scales is increasing in importance. To address this, we have developed a dynamic force microscopy technique where the flexure of the microcantilever is excited using an intensity modulated laser beam to achieve modulation on the picoscale. The flexure arises from thermally induced bending through differential expansion and the conservation of momentum when the photons are reflected and absorbed by the cantilever. In this study, we investigated the photothermal and photon pressure responses of monolithic and layered cantilevers using a modulated laser in air and immersed in water. The developed photon actuation technique is applied to the stretching of single polymer chains.

Physical properties of phase-change emulsions.

Phase-change emulsions (PCE) are important in a variety of applications, from ultrasound imaging to the explosive material used in the mining industry, but until now there has been no adequate theory to describe their activation properties. The PCE consists of a low-boiling-point liquid, known as the volatile phase, dispersed in an aqueous phase. The volatile phase boils as a result of an increase in the temperature of the emulsion. The volume of the emulsion will increase during this phase transition, with the transition temperature and final volume of the emulsion highly dependent on the initial radius of the liquid droplets. Here a description of the change in boiling point and freezing point of the volatile phase, as well as the volume change of a droplet in the emulsion as a function of the initial droplet radius, is presented. The influence of volatile phase solubility, liquid-liquid interfacial tension, and final temperature are explored, accounting for the influence of confinement on the properties of the volatile phase. Beyond this, a means by which the diffusivity of the gas in the continuous liquid phase can be measured is derived.