Schottky barriers to semiconducting polymers

Schottky barrier diodes are made from virtually all semiconducting polymers. Application of Schottky barriers on the development of electronic devices built from semiconducting polymers prompted this research. The article investigated the dc and ac admittance of Schottky barrier which occur at the interface between aluminum and poly(3-methyl thiophene) made ready by electropolymerisation. The experiment revealed that the interfacial layers occurring in polymer Schottky barriers is significant in the response of the controlling device.

Electrical study of impurity states in conjugated polymers

Schottky diodes resulting from an intimate contact of aluminum on electro-deposited poly(3-methylthiopene), PMeT, have been studied by admittance spectroscopy, capacitance-voltage and current-voltage measurements, and optically-induced current transients. The loss-tangents show the existence of interface states that can be removed by vacuum annealing, also visible in the transients. Furthermore, the CV curves don't substantiate the idea of movement of the dopant ions.

Electrical characterization of semiconducting polymers

Schottky diodes resulting from an intimate contact of aluminum on electrodeposited poly(3-methylthiopene) were studied by admittance spectroscopy, capacitance-voltage measurements and voltaic and optically-induced current and capacitance transients. The loss tangents show the existence of interface states that can be removed by vacuum annealing. Furthermore, the C-V curves contradict the idea of movement of the dopant ions.

Schottky barrier diodes from semiconducting polymers

Schottky barrier diodes based on Al/poly(3-methylthiophene)/Au have been fabricated and their electrical behaviour investigated. I-V characteristics revealed a dependence on the fabrication conditions, specifically on the time under vacuum prior to evaporation of the rectifying contact and post-metal annealing at elevated temperature. The available evidence is consistent with the formation of a thin insulating layer between the metal and the polymer following these procedures. Long periods under vacuum prior to deposition of the aluminium electrode reduced the likelihood of such a layer forming. Capacitance-voltage plots of the devices were stable to voltage cycling, so long as the forward voltage did not exceed similar to 1 V. Above this a small degree of hysteresis was observed, which is attributed to the filling/emptying of interface states or traps in the polymer.

Ammonia effects on proton conductivity properties of coordination polymers

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

Comb polymers: are they the answer to monolayer stability?

Molecular monolayers reduce the amount of water lost to evaporation due to their ability to form closely packed films at the air-water interface. However, they are susceptible to loss from the water surface and poor performance on exposure to wind. This study combines experimental and theoretical techniques to investigate the properties of a small molecule monolayer mixed with comb polymers. The study reveals that at high concentrations of polymer the monolayer exhibits increased mechanical stability which improves the resistance to disruption by wind. Inclusion of hydrophilic functional groups along the backbone of the polymer leads to further improvements in wind stability. However, the improved wind stability observed in the composites comes at the expense of poorer water evaporation resistance.

Formation of dynamic duolayer systems at the air/water interface by using non-ionic hydrophilic polymers

The inclusion of a water-soluble polymer, poly(vinyl pyrrolidone) (PVP), into a surface active film composition before application to the water surface leads to the formation of a dynamic duolayer; a novel surface film system. This duolayer shows improved surface viscosity over the monolayer compound alone, while the addition of polymer maintains other film properties such as evaporation control and equilibrium spreading pressure. Brewster Angle Microscopy shows that the duolayer film undergoes a different formation mechanism upon film compression, and the resultant surface pressure/area isotherm is different at lower surface pressures indicating the PVP is present on the water surface at these pressures and squeezed out to the water subphase at higher pressures. The addition of water-soluble polymers to form a dynamic duolayer provides a unique way to produce defect-free and tightly packed films while polymer is associated with the film. This finding provides new knowledge for the design of surface films with improved properties with potential applications in many areas.

Perspectives of engineered marine derived polymers for biomedical nanoparticles

Marine environment exhibits an enormous diversity of organisms which contains an abundant source of polysaccharides. As polymer matrix carriers, marine-based polymers possess several valuable properties including high stability, non-toxicity, hydrophilicity, biodegradability, with low production cost. Despite notable biological activities of these natural polymers, there are certain limitations in exploring their functions in applications of nano-sized drug delivery systems. The review aims to demonstrate exceptional characteristics of marine-based polymers including fucoidan, alginate, carrageenan, hyaluronic acid, chondroitin sulfate, and chitosan as well as provide perspectives of current publications on their nanoparticle formulations for biomedical applications.

Crack damage in polymers and composites: a review

Polymer-based materials are extensively used in various applications such as aircrafts, civilian structures, oil and gas platforms and electronics. They are, however, inherently damage prone and over time, the formation of cracks and microscopic damages influences the thermo-mechanical and electrical properties, which eventually results in the total failure of the materials. This paper provides an overview of the principal causes of cracking in polymer and composites and summarizes the recent progress in the development of non-destructive techniques in crack detection. Furthermore, recent progress in the development of bio-inspired self-healing methods in autonomic repair is discussed.

Aerobic fermentation of saccharomeyes cerevisae in a miniature bioreactor made of low cost poly(methylmethacrylate) (PMMA) and poly(Dimethylsiloxane) (PDMS) polymers

In this paper, a minibioreactor platform made of low cost polymers is presented. The minibioreactor prototype was designed as an alternative solution for carrying out microbial fermentation experiments in laboratory. The minibioreactor prototype has a working volume of 1.5 mL and was fabricated from poly(methylmethacrylate) (PMMA) and poly(dimethylsiloxane) (PDMS) polymers. Cell density was measured online whilst agitation rates and the temperature of the reactor content can be tightly controlled to desired set-point values. As proof-of-concept, various S. cerevisae fermentation experiments were conducted. In every experiment, the minibioreactor operated stably for the entire length of operation which was nearly 40 h with very minimal volume loss i.e. about 2.8 μ·h-1 at 37°C. The minibioreactor has the maximum oxygen transfer rate (OTR) of 16.6 mmol·L-1·h-1 under the agitation rate of 300 rpm. Under these conditions, cell specific growth rate as high as 0.291 h-1 was obtained. The experimental data in the minibioreactor operation was also reproducible using shake flask where similar growth profiles were attained under a similar growth conditions.

A robust and reproducible procedure for cross-linking thermoset polymers using molecular simulation

Molecular simulation can provide valuable guidance in establishing clear links between structure and function to enable the design of new polymer-based materials. However, molecular simulation of thermoset polymers in particular, such as epoxies, present specific challenges, chiefly in the credible preparation of polymerised samples. Despite this need, a comprehensive, reproducible and robust process for accomplishing this using molecular simulation is still lacking. Here, we introduce a clear and reproducible cross-linking protocol to reliably generate three dimensional epoxy cross-linked polymer structures for use in molecular simulations. This protocol is sufficiently detailed to allow complete reproduction of our results, and is applicable to any general thermoset polymer. Amongst our developments, key features include a reproducible procedure for calculation of partial atomic charges, a reliable process for generating and validating an equilibrated liquid precursor mixture, and establishment of a novel, robust and reproducible protocol for generating the three-dimensional cross-linked solid polymer. We use these structures as input to subsequent molecular dynamics simulations to calculate a range thermo-mechanical properties, which compare favourably with experimental data. Our general protocol provides a benchmark for the process of simulating epoxy polymers, and can be readily translated to prepare and model epoxy samples that are dynamically cross-linked in the presence of surfaces and nanostructures.

The creation and evaluation of novel canine training aids for cocaine using molecularly encapsulated sol-gel polymers and an investigation of canine field accuracy

Biological detectors, such as canines, are valuable tools used for the rapid identification of illicit materials. However, recent increased scrutiny over the reliability, field accuracy, and the capabilities of each detection canine is currently being evaluated in the legal system. For example, the Supreme Court case, State of Florida v. Harris, discussed the need for continuous monitoring of canine abilities, thresholds, and search capabilities. As a result, the fallibility of canines for detection was brought to light, as well as a need for further research and understanding of canine detection. This study is two-fold, as it looks to not only create new training aids for canines that can be manipulated for dissipation control, but also investigates canine field accuracy to objects with similar odors to illicit materials. ^ It was the goal of this research to improve upon current canine training aid mimics. Sol-gel polymer training aids, imprinted with the active odor of cocaine, were developed. This novel training aid improved upon the longevity of currently existing training aids, while also provided a way to manipulate the polymer network to alter the dissipation rate of the imprinted active odors. The manipulation of the polymer network could allow handlers to control the abundance of odors presented to their canines, familiarizing themselves to their canine’s capabilities and thresholds, thereby increasing the canines’ strength in court.^ The field accuracy of detection canines was recently called into question during the Supreme Court case, State of Florida v. Jardines, where it was argued that if cocaine’s active odor, methyl benzoate, was found to be produced by the popular landscaping flower, snapdragons, canines will false alert to said flowers. Therefore, snapdragon flowers were grown and tested both in the laboratory and in the field to determine the odors produced by snapdragon flowers; the persistence of these odors once flowers have been cut; and whether detection canines will alert to both growing and cut flowers during a blind search scenario. Results revealed that although methyl benzoate is produced by snapdragon flowers, certified narcotics detection canines can distinguish cocaine’s odor profile from that of snapdragon flowers and will not alert.^

Synthetic approaches to flexible fluorescent conjugated polymers

Conjugated polymers (CPs) are intrinsically fluorescent materials that have been used for various biological applications including imaging, sensing, and delivery of biologically active substances. The synthetic control over flexibility and biodegradability of these materials aids the understanding of the structure-function relationships among the photophysical properties, the self-assembly behaviors of the corresponding conjugated polymer nanoparticles (CPNs), and the cellular behaviors of CPNs, such as toxicity, cellular uptake mechanisms, and sub-cellular localization patterns. ^ Synthetic approaches towards two classes of flexible CPs with well-preserved fluorescent properties are described. The synthesis of flexible poly( p-phenylenebutadiynylene)s (PPBs) uses competing Sonogashira and Glaser coupling reactions and the differences in monomer reactivity to incorporate a small amount (∼10%) of flexible, non-conjugated linkers into the backbone. The reaction conditions provide limited control over the proportion of flexible monomer incorporation. Improved synthetic control was achieved in a series of flexible poly(p-phenyleneethynylene)s (PPEs) using modified Sonogashira conditions. In addition to controlling the degree of flexibility, the linker provides disruption of backbone conjugation that offers control of the length of conjugated segments within the polymer chain. Therefore, such control also results in the modulation of the photophysical properties of the materials. ^ CPNs fabricated from flexible PPBs are non-toxic to cells, and exhibit subcellular localization patterns clearly different from those observed with non-flexible PPE CPNs. The subcellular localization patterns of the flexible PPEs have not yet been determined, due to the toxicity of the materials, most likely related to the side-chain structure used in this series. ^ The study of the effect of CP flexibility on self-assembly reorganization upon polyanion complexation is presented. Owing to its high rigidity and hydrophobicity, the PPB backbone undergoes reorganization more readily than PPE. The effects are enhanced in the presence of the flexible linker, which enables more efficient π-π stacking of the aromatic backbone segments. Flexibility has minimal effects on the self-assembly of PPEs. Understanding the role of flexibility on the biophysical behaviors of CPNs is key to the successful development of novel efficient fluorescent therapeutic delivery vehicles.^

Microporous organic polymers based on hexaphenylbiadamantane:synthesis, ultra-high stability and gas capture

Hexaphenylbiadamantane-based microporous organic polymers (MOPs) were successfully synthesized by Suzuki coupling under mild conditions. The obtained MOPs show high surface area (891 m2 g−1), ultra-high thermal (less than 40% mass loss at temperatures up to 1000 °C) and chemical (no apparent decomposition in organic solvents for more than 7 days) stability, gas (H2, CO2, CH4) capture capabilities and vapor (benzene, hexane) adsorption. These combined abilities render the synthesized MOPs an attractive candidate as thermo-chemically stable adsorbents for practical use in gas storage and pollutant vapor adsorption.

Designing intrinsically photostable low band gap polymers:a smart tool combining EPR spectroscopy and DFT calculations

A rapid and efficient method to identify the weak points of the complex chemical structure of low band gap (LBG) polymers, designed for efficient solar cells, when submitted to light exposure is reported. This tool combines Electron Paramagnetic Resonance (EPR) using the 'spin trapping method' coupled with density functional theory modelling (DFT). First, the nature of the short life-time radicals formed during the early-stages of photo-degradation processes are determined by a spin-trapping technique. Two kinds of short life-time radical (R and R′O) are formed after 'short-duration' illumination in an inert atmosphere and in ambient air, respectively. Second, simulation allows the identification of the chemical structures of these radicals revealing the most probable photochemical process, namely homolytical scission between the Si atom of the conjugated skeleton and its pendent side-chains. Finally, DFT calculations confirm the homolytical cleavage observed by EPR, as well as the presence of a group that is highly susceptible to photooxidative attack. Therefore, the synergetic coupling of a spin trapping method with DFT calculations is shown to be a rapid and efficient method for providing unprecedented information on photochemical mechanisms. This approach will allow the design of LBG polymers without the need to trial the material within actual solar cell devices, an often long and costly screening procedure.