PEDOT:PSS self-assembled films to methanol crossover reduction in Nafion (R) membranes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Caracterização e aplicação da Blenda PEDOT : PSS/PVA na construção de eletrodos transparentes e dispositivos eletroluminescentes

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Nanoindentazione di film sottili di PEDOT:PSS su substrato rigido

In questa tesi vengono presentati i risultati sperimentali di nanoindentazione su film sottili di PEDOT:PSS depositato su substrato rigido (vetro). Nella prima parte viene presentato lo sviluppo della teoria classica sul contatto meccanico tra due superfici elastiche, sviluppata per la prima volta da Hertz nella seconda metà dell'Ottocento. Nel Capitolo 2 si entra maggiormente nel dettaglio con la spiegazione del metodo sviluppato da Oliver e Pharr per misurare alcune proprietà meccaniche dei materiali tramite la tecnica della nanoindentazione utilizzata in questo esperimento. Particolare riguardo viene dato al modo in cui vengono misurate le quantità fisiche rilevanti, ovvero modulo di Young e durezza. Nel terzo capitolo vengono descritte brevemente la struttura del polimero PEDOT:PSS e la tecnica utilizzata per sintetizzarlo a partire dal suo monomero, l'EDOT. Nel Capitolo 4 una sezione è dedicata alla descrizione della preparazione dei campioni di PEDOT:PSS utilizzati in questo esperimento, quindi una parte è dedicata alla descrizione dello strumento di misura, mentre la restante parte del capitolo è riservata alla presentazione dei risultati sperimentali con l'aiuto di grafici e tabelle. Nella parte finale di questo lavoro si riportano alcune conclusioni sui risultati ottenuti.

Caratterizzazione di film sottili di PEDOT:PSS

Negli ultimi 20 anni lo studio dei materiali organici dalle proprietà conduttive si è ampliato significativamente in un range di applicazioni molto vasto, che va dall'assemblaggio e costruzione di sistemi microelettronici avanzati ad applicazioni nel campo della bioelettronica e dell'ingegneria biomedica. Il presente lavoro rappresenta un punto d'incontro tra la fisica dei materiali e la ricerca in ambito biomedico e verte sullo studio delle particolari proprietà del poli(3,4-etilenediossitiofene) drogato con poli(stirene sulfonato), o PEDOT:PSS, utilizzato nella preparazione di substrati per colture cellulari. Nel primo capitolo, di natura descrittiva, viene presentata una panoramica sui polimeri conduttivi e sulle loro caratteristiche principali con particolare approfondimento sul PEDOT:PSS e sulle sue applicazioni in ambito di ricerca. Il secondo capitolo contiene una descrizione approfondita della strumentazione e delle procedure utilizzati per la caratterizzazione dei campioni: sommariamente, questi comprendono misure di resistenza superficiale, di angolo di contatto e analisi morfologiche tramite AFM. Nel terzo e ultimo capitolo vengono esposte le tecniche di preparazione dei campioni e vengono mostrati e discussi i risultati delle misure eseguite sui campioni preparati.

PEDOT:PSS thin films: Applications in Bioelectronics

Owing to their capability of merging the properties of metals and conventional polymers, Conducting Polymers (CPs) are a unique class of carbon-based materials capable of conducting electrical current. A conjugated backbone is the hallmark of CPs, which can readily undergo reversible doping to different extents, thus achieving a wide range of electrical conductivities, while maintaining mechanical flexibility, transparency and high thermal stability. Thanks to these inherent versatility and attracting properties, from their discovery CPs have experienced incessant widespread in a great plethora of research fields, ranging from energy storage to healthcare, also encouraging the spring and growth of new scientific areas with highly innovative content. Nowadays, Bioelectronics stands out as one of the most promising research fields, dealing with the mutual interplay between biology and electronics. Among CPs, the polyelectrolyte complex poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate) (PEDOT:PSS), especially in the form of thin films, has been emphasized as ideal platform for bioelectronic applications. Indeed, in the last two decades PEDOT:PSS has played a key role in the sensing of bioanalytes and living cells interfacing and monitoring. In the present work, development and characterization of two kinds of PEDOT:PSS-based devices for applications in Bioelectronics are discussed in detail. In particular, a low-cost amperometric sensor for the selective detection of Dopamine in a ternary mixture was optimized, taking advantage of the electrocatalytic and antifouling properties that render PEDOT:PSS thin films appealing tools for electrochemical sensing of bioanalytes. Moreover, the potentialities of this material to interact with live cells were explored through the fabrication of a microfluidic trapping device for electrical monitoring of 3D spheroids using an impedance-based approach.

ZnO flower/PEDOT:PSS thermoelectric composite films

ZnO flower/poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) composite films were prepared by spin-coating dimethyl sulfoxide doped PEDOT:PSS on the ZnO flowers grown on glass substrate. The thermoelectric properties of the ZnO flower/PEDOT:PSS composite films were measured at room temperature. As the number of spin coated PEDOT:PSS layer increased, the electrical conductivity of the ZnO flower/PEDOT:PSS composite films increases dramatically from 1-layer (177.3 S/m) to 4-layer (910.4 S/m), however, all the composite films have almost the same Seebeck coefficient (~20–22 μV/K). A maximum power factor of ~0.4 μWm−1 K−2 at room temperature was obtained from the composite film with 4-layer PEDOT:PSS.

PEDOT:PSS: un polimero conduttivo organico per lo studio dell'integrità del tessuto cellulare

Questa tesi si inserisce nel campo della Bioelettronica Organica con lo scopo di utilizzare dei transistor elettrochimici (OECT) organici basati sul polimero conduttivo PEDOT:PSS per rilevare l’integrità di un tessuto cellulare e come biosensori di analiti in soluzione. Nella prima parte dell’elaborato, si spiegano le proprietà ed il trasporto di carica dei polimeri coniugati concentrandosi sulle caratteristiche fisico chimiche del PEDOT:PSS, seguito da una trattazione analitica del principio di funzionamento di un OECT. La seconda parte, si concentra sul lavoro sperimentale partendo da una descrizione dei processi di fabbricazione degli OECT, dei metodi di caratterizzazione utilizzati e della progettazione del set-up sperimentale per permettere le misure elettriche nell’incubatore cellulare. In seguito, viene dimostrato l’uso di un OECT completamente a base di PEDOT:PSS come sensore di un neurotrasmettitore (dopamina). In parallelo, il lavoro si è concentrato sull’ottimizzazione dei transistor in termini di formulazione di PEDOT:PSS e di geometria del dispositivo per ottenere tempi di spegnimento veloci compatibili con le risposte cellulari (<300ms). In fase di preparazione alle misure con le cellule si è valutato la funzionalità dell’OECT nelle condizioni di coltura cellulare dimostrando una buona stabilità dei dispositivi. Inoltre, sono stati progettati degli studi di simulazione tramite una membrana porosa per prevedere le risposte dei transistor in presenza di un tessuto cellulare. Partendo dall’esito positivo dei test preliminari, il lavoro si è concluso con il primo esperimento con le cellule tumorali HeLa, in cui si è monitorata la crescita cellulare con immagini ottiche correlate alle misure elettriche. I primi risultati confermano la biocompatibilità dei dispositivi e una risposta elettrica degli OECTs alla presenza delle cellule, aprendo la possibilità di utilizzare questi dispositivi per futuri esperimenti anche con diversi tipi di cellule.

Electrochromic, magnetotransport and AC transport properties of vapor phase polymerized PEDOT(VPP PEDOT)

Poly(3,4-ethylenedioxy)thiophene (PEDOT) doped with tosylate ion (PEDOT-tosylate or VPP PEDOT) was synthesized by vapor phase polymerization (VPP) technique on glass as well as on glass/ITO and the electrochromic properties were investigated. Compared with that of PEDOT-PSS spin-coated on glass/ITO, the studies showed that VPP PEDOT has a lower work function and better electrochromic properties. The magneto and AC transport properties studies were done on VPP PEDOT coated on glass substrate. The system shows 2-dimensional variable range hopping and wave function shrinkage of charge carriers.

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.

Exploiting high quality PEDOT:PSS–SWNT composite formulations for wet-spinning multifunctional fibers

In order to exploit the inherent properties of carbon nanotubes (CNT) in any polymer composite, systematic control of carbon nanotube loading and protocols that mitigate against CNT bundling are required. If such composites are to be rendered in fiber form via wet-spinning, then CNT bundling during the coagulation process must also be avoided. Here we have achieved this by utilizing highly exfoliated single walled carbon nanotubes (SWNT) and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonicacid) (PEDOT:PSS) to obtain wet-spinnable composite formulations at various nanotube volume fractions (Vf). The addition of only 0.02 Vf of aggregate-free and individually dispersed SWNT resulted in a significant enhancement of modulus, tensile strength, electrical conductivity and two cell electrode specific capacitance of PEDOT:PSS–SWNT composite fibers to 5.2 GPa, 200 MPa, 450 S cm−1 and 59 F g−1 by the rate of dY/dVf = 89 GPa, dσ/dVf = 3.2 GPa, dS/dVf = 13 300 S cm−1 and 6 folds, respectively.

Stable organic photovoltaics using Ag thin film anodes

The interaction at the interface between a metal electrode and photoactive polymer is crucial for overall performance and stability of organic photovoltaics (OPVs). In this article, we report a comparative study of the stability of thin film Ag and indium tin oxide (ITO) as electrodes when used in conjunction with an interfacial PEDOT:PSS layer for P3HT:PCBM blend OPV devices. XPS measurements were taken for Ag and ITO/PEDOT:PSS layered samples with different exposure times to ambient conditions (∼25 °C, ∼50% relative humidity) to investigate the migration of Ag and In into the PEDOT:PSS layer. The change in efficiency of OPVs with a longer exposure time and degree of migration is explained by the analysis of XPS results. We propose the mechanism behind the interactions occurring at the interfaces. The efficiency of the ITO electrode OPVs continuously decreased to below 10% of the initial efficiency. However, the Ag devices displayed a slower degradation and maintained 50% of the initial efficiency for the same period of time.

Pathway to high throughput, low cost indium-free transparent electrodes

A roll-to-roll compatible, high throughput process is reported for the production of highly conductive, transparent planar electrode comprising an interwoven network of silver nanowires and single walled carbon nanotubes imbedded into poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS). The planar electrode has a sheet resistance of between 4 and 7 Ω □−1 and a transmission of >86% between 800 and 400 nm with a figure of merit of between 344 and 400 Ω−1. The nanocomposite electrode is highly flexible and retains a low sheet resistance after bending at a radius of 5 mm for up to 500 times without loss. Organic photovoltaic devices containing the planar nanocomposite electrodes had efficiencies of ∼90% of control devices that used indium tin oxide as the transparent conducting electrode.

Charge transport in transparent conductors: A comparison

A comparative investigation of charge transport properties is presented, for polymeric [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)], single-wall carbon nanotube (SWNT) and inorganic (indium tin oxide, ITO), transparent conducting electrodes. The polymeric and nanotube systems show hopping transport at low temperatures, in contrast with the disordered-metal transport in ITO. The low temperature magnetotransport (up to 11 T) and high electric-field transport (up to 500 V/cm) indicate the significant role of nanoscopic scale disorder for charge transport in polymer and nanotube based systems. The results show that characteristic length scales like localization length correlates with the nanomorphology in these systems. Further, the high frequency conductivity measurements (up to 30 MHz) in PEDOT:PSS and SWNT follow the extended pair approximation model [σ(ω)=σ(0)[1+(ω/ω0)s].

Modified conformation and physical properties in conducting polymers due to varying conjugation and solvent interactions

Small angle X-ray scattering (SAXS) studies of poly2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) with varying conjugation, and polyethylene dioxythiophene complexed with polystyrene sulfonate (PEDOT-PSS) in different solvents have shown the importance of the role of pi-electron conjugation and solvent-chain interactions in controlling the chain conformation and assembly. In MEH-PPV, by increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in the fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. In the case of PEDOT-PSS, the chains undergo solvent induced expansion and enhanced chain organization. The clusters formed by chains are better correlated in dimethyl sulfoxide (DMSO) solution than water, as observed in the scattered intensity profiles. The values of radius of gyration and the exponent (water: 2.6, DMSO: 2.31) of power-law decay, obtained from the unified scattering function (Beaucage) analysis, give evidence for chain expansion from compact (in water) to an extended coil in DMSO solutions, which is consistent with the Kratky plot analysis. The mechanism of this transition and the increase in dc conductivity of PEDOT-PSS in DMSO solution are discussed. The onset frequency for the increase in ac conduction, as well as its temperature dependence, probes the extent of the connectivity in the PEDOT-PSS system. The enhanced charge transport in PEDOT-PSS in DMSO is attributed to the extended chain conformation, as observed in the SAXS results.