Optical investigations of the effect of solvent and thermal annealing on the optoelectronic properties of Poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) films

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is one of the most promising conducting polymers that can be used as transparent electrode or as buffer layer for organic electronic devices. However, when used as an electrode, its conductivity has to be optimized either by the addition of solvents or by post-deposition processing. In this work, we investigate the effect of the addition of the polar solvent dimethylsulfoxide (DMSO) to an aqueous PEDOT:PSS solution on its optical and electrical properties by the implementation of the Drude model for the analysis of the measured pseudo-dielectric function by Spectroscopic Ellipsometry from the near infrared to the visible-far ultraviolet spectral range. The results show that the addition of DMSO increases significantly the film conductivity, which reaches a maximum value at an optimum DMSO concentration as it has confirmed by experimentally measured conductivity values. The post-deposition thermal annealing has been found to have a smaller effect on the film conductivity. © 2013 Elsevier B.V.

Performance of hybrid buffer Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) layers doped with plasmonic silver nanoparticles

We compare the performance of a typical hole transport layer for organic photovoltaics (OPVs), Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) thin film with a series of PEDOT:PSS layers doped with silver (Ag) nanoparticles (NPs) of various size distributions. These hybrid layers have attracted great attention as buffer layers in plasmonic OPVs, although there is no report up to date on their isolated performance. In the present study we prepared a series of PEDOT:PSS layers sandwiched between indium tin oxide (ITO) and gold (Au) electrodes. Ag NPs were deposited on top of the ITO by electron beam evaporation followed by spin coating of PEDOT:PSS. Electrical characterization performed in the dark showed linear resistive behavior for all the samples; lower resistance was observed for the hybrid ones. It was found that the resistivity of the samples decreases with increasing the particle's size. A substantial increase of the electric field between the ITO and the Au electrodes was seen through the formation of current paths through the Ag NPs. A striking observation is the slight increase in the slope of the current density versus voltage curves when measured under illumination for the case of the plasmonic layers, indicating that changes in the electric field in the vicinity of the NP due to plasmonic excitation is a non-vanishing factor. © 2014 Published by Elsevier B.V. All rights reserved.

La 0.7Ca 0.3MnO 3 / Mn 3O 4 composites: Does an insulating secondary phase always enhance the low field magnetoresistance of manganites

Composites of magnetoresistive La 0.7Ca 0.3MnO 3 (LCMO) with insulating Mn 3O 4 are useful as a model system because no foreign cation is introduced in the LCMO phase by interdiffusion during the heat treatment. Here we report the magnetotransport properties as a function of sintering temperature T sinter for a fixed LCMO/Mn 3O 4 ratio. Decreasing T sinter from 1250 °C to 800 °C causes an increase in low field magnetoresistance (LFMR) that correlates with the decrease in crystallite size (CS) of the LCMO phase. When plotting LFMR at (77 K, 0.5 T) versus 1/CS, we find that the data for the LCMO/Mn 3O 4 composites sintered between 800 °C and 1250 °C follow the same trend line as data from the literature for pure LCMO samples with crystallite size >∼25 nm. This differs from the LFMR enhancement observed by many authors in the usual manganite composites, i.e., composites where the insulating phase contains cations other than La, Ca or Mn. This difference suggests that diffusion of foreign cations into the grain boundary region is a necessary ingredient for the enhanced LFMR. © 2012 American Institute of Physics.

Magnetocaloric effect in nano- and polycrystalline manganite $La_{0.7}Ca_{0.3}MnO_3$

$La_{0.7}Ca_{0.3}MnO_3$ samples were prepared in nano- and polycrystalline forms by sol-gel and solid state reaction methods, respectively, and structurally characterized by synchrotron X-ray diffraction. The magnetic properties determined by ac susceptibility and dc magnetization measurements are discussed. The magnetocaloric effect in this nanocrystalline manganite is spread over a broader temperature interval than in the polycrystalline case. The relative cooling power of the poly- and nanocrystalline manganites is used to evaluate a possible application for magnetic cooling below room temperature.

Nanoengineering coaxial carbon nanotube-dual-polymer heterostructures.

We describe studies of new nanostructured materials consisting of carbon nanotubes wrapped in sequential coatings of two different semiconducting polymers, namely, poly(3-hexylthiophene) (P3HT) and poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT). Using absorption spectroscopy and steady-state and ultrafast photoluminescence measurements, we demonstrate the role of the different layer structures in controlling energy levels and charge transfer in both solution and film samples. By varying the simple solution processing steps, we can control the ordering and proportions of the wrapping polymers in the solid state. The resulting novel coaxial structures open up a variety of new applications for nanotube blends and are particularly promising for implementation into organic photovoltaic devices. The carbon nanotube template can also be used to optimize both the electronic properties and morphology of polymer composites in a much more controlled fashion than achieved previously, offering a route to producing a new generation of polymer nanostructures.

Bioelectronics meets nanomedicine for cardiovascular implants: PEDOT-based nanocoatings for tissue regeneration.

BACKGROUND: An exciting direction in nanomedicine would be to analyze how living cells respond to conducting polymers. Their application for tissue regeneration may advance the performance of drug eluting stents by addressing the delayed stent re-endothelialization and late stent thrombosis. METHODS: The suitability of poly (3, 4-ethylenedioxythiophene) (PEDOT) thin films for stents to promote cell adhesion and proliferation is tested in correlation with doping and physicochemical properties. PEDOT doped either with poly (styrenesulfonate) (PSS) or tosylate anion (TOS) was used for films' fabrication by spin coating and vapor phase polymerization respectively. PEGylation of PEDOT: TOS for reduced immunogenicity and biofunctionalization of PEDOT: PSS with RGD peptides for induced cell proliferation was further applied. Atomic Force Microscopy and Spectroscopic Ellipsometry were implemented for nanotopographical, structural, optical and conductivity measurements in parallel with wettability and protein adsorption studies. Direct and extract testing of cell viability and proliferation of L929 fibroblasts on PEDOT samples by MTT assay in line with SEM studies follow. RESULTS: All PEDOT thin films are cytocompatible and promote human serum albumin adsorption. PEDOT:TOS films were found superior regarding cell adhesion as compared to controls. Their nanotopography and hydrophilicity are significant factors that influence cytocompatibility. PEGylation of PEDOT:TOS increases their conductivity and hydrophilicity with similar results on cell viability with bare PEDOT:TOS. The biofunctionalized PEDOT:PSS thin films show enhanced cell proliferation. CONCLUSIONS: The application of PEDOT polymers has evolved as a new perspective to advance stents. GENERAL SIGNIFICANCE: In this work, nanomedicine involving nanotools and novel nanomaterials merges with bioelectronics to stimulate tissue regeneration for cardiovascular implants. This article is part of a Special Issue entitled Organic Bioelectronics - Novel Applications in Biomedicine.

Effects of buffer layer properties and annealing process on bulk heterojunction morphology and organic solar cell performance

The performance of polymer-fullerene bulk heterojunction (BHJ) solar cells is strongly dependent on the vertical distribution of the donor and acceptor regions within the BHJ layer. In this work, we investigate in detail the effect of the hole transport layer (HTL) physical properties and the thermal annealing on the BHJ morphology and the solar cell performance. For this purpose, we have prepared solar cells with four distinct formulations of poly(3,4- ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) buffer layers. The samples were subjected to thermal annealing, applied either before (pre-annealing) or after (post-annealing) the cathode metal deposition. The effect of the HTL and the annealing process on the BHJ ingredient distribution - namely, poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) - has been studied by spectroscopic ellipsometry and atomic force microscopy. The results revealed P3HT segregation at the top region of the films, which had a detrimental effect on all pre-annealed devices, whereas PCBM was found to accumulate at the bottom interface. This demixing process depends on the PEDOT:PSS surface energy; the more hydrophilic the surface the more profound is the vertical phase separation within the BHJ. At the same time those samples suffer from high recombination losses as evident from the analysis of the J-V measurements obtained in the dark. Our results underline the significant effect of the HTL-active and active-ETL (electron transport layer) interfacial composition that should be taken into account during the optimization of all polymer-fullerene solar cells. © 2012 The Royal Society of Chemistry.

Substrate treatment and drying conditions effect on the properties of roll-to-roll gravure printed PEDOT:PSS thin films

The optical, structural and electrical properties of poly(3,4- ethylenedioxythiophene):poly(4-styrenesulfonic acid) (PEDOT:PSS) thin films printed by roll-to-roll gravure have been investigated. Corona treatment has been applied to enhance the adhesion of PEDOT:PSS on PolyEthylene Terephthalate (PET) web. It has been found that there was a stronger in-depth surface modification of PET with the increase of corona efficiency; however, the adhesion of PEDOT:PSS was not actually affected. Also, Spectroscopic Ellipsometry and Atomic Force Microscopy have been used to extract information on the mechanisms that define PEDOT:PSS properties. The increase of the drying temperature of the PEDOT:PSS films has been found to reduce the remaining water inside the films and lead to the decrease of the PEDOT:PSS particles size. © 2011 Elsevier B.V. All rights reserved.

Experimental evaluation of layout designs for 3 × 3 MIMO-enabled radio-over-fiber distributed antenna systems

This paper experimentally demonstrates that, for two representative indoor distributed antenna system (DAS) scenarios, existing radio-over-fiber (RoF) DAS installations can enhance the capacity advantages of broadband 3 × 3 multiple-input-multiple-output (MIMO) radio services without requiring additional fibers or multiplexing schemes. This is true for both single-and multiple-user cases with a single base station and multiple base stations. First, a theoretical example is used to illustrate that there is a negligible improvement in signal-to-noise ratio (SNR) when using a MIMO DAS with all N spatial streams replicated at N RAUs, compared with a MIMO DAS with only one of the N streams replicated at each RAU for N ≤ 4. It is then experimentally confirmed that a 3 × 3 MIMO DAS offers improved capacity and throughput compared with a 3 × 3 MIMO collocated antenna system (CAS) for the single-user case in two typical indoor DAS scenarios, i.e., one with significant line-of-sight (LOS) propagation and the other with entirely non-line-of-sight (NLOS) propagation. The improvement in capacity is 3.2% and 4.1%, respectively. Then, experimental channel measurements confirm that there is a negligible capacity increase in the 3 × 3 configuration with three spatial streams per antenna unit over the 3 × 3 configuration with a single spatial stream per antenna unit. The former layout is observed to provide an increase of ∼1% in the median channel capacity in both the single-and multiple-user scenarios. With 20 users and three base stations, a MIMO DAS using the latter layout offers median aggregate capacities of 259 and 233 bit/s/Hz for the LOS and NLOS scenarios, respectively. It is concluded that DAS installations can further enhance the capacity offered to multiple users by multiple 3 × 3 MIMO-enabled base stations. Further, designing future DAS systems to support broadband 3 × 3 MIMO systems may not require significant upgrades to existing installations for small numbers of spatial streams. © 2013 IEEE.

Graphene nanoribbon blends with P3HT for organic electronics.

In organic field-effect transistors (OFETs) the electrical characteristics of polymeric semiconducting materials suffer from the presence of structural/morphological defects and grain boundaries as well as amorphous domains within the film, hindering an efficient transport of charges. To improve the percolation of charges we blend a regioregular poly(3-hexylthiophene) (P3HT) with newly designed N = 18 armchair graphene nanoribbons (GNRs). The latter, prepared by a bottom-up solution synthesis, are expected to form solid aggregates which cannot be easily interfaced with metallic electrodes, limiting charge injection at metal-semiconductor interfaces, and are characterized by a finite size, thus by grain boundaries, which negatively affect the charge transport within the film. Both P3HT and GNRs are soluble/dispersible in organic solvents, enabling the use of a single step co-deposition process. The resulting OFETs show a three-fold increase in the charge carrier mobilities in blend films, when compared to pure P3HT devices. This behavior can be ascribed to GNRs, and aggregates thereof, facilitating the transport of the charges within the conduction channel by connecting the domains of the semiconductor film. The electronic characteristics of the devices such as the Ion/Ioff ratio are not affected by the addition of GNRs at different loads. Studies of the electrical characteristics under illumination for potential use of our blend films as organic phototransistors (OPTs) reveal a tunable photoresponse. Therefore, our strategy offers a new method towards the enhancement of the performance of OFETs, and holds potential for technological applications in (opto)electronics.