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Electroactive Conjugated Polyelectrolytes Based on EDOT From Synthesis to Organic Electronics
Linköping University, Department of Physics, Chemistry and Biology, Organic Chemistry. Linköping University, The Institute of Technology.
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Conjugated polyelectrolytes (CP) show interesting electrical and optical properties for organic electronics as well as for life science applications. Their possibilities of supramolecular assembly with nanowire like misfolded proteins, amyloids, as well as synthetic polypeptides or DNA forming conducting nano composites is highly interesting as being a truly bottom up approach for fabrication of OLEDs, photovoltaic’s as well as logic devices.

A special class of CPs is that of electroactive cojugated polymers (ECPs), which, due to their structure, will exhibits a unique combination of properties, including the following; electrically conducting, ability to store an electric charge and ability to exchange ions. The positive or negative excess charge can be introduced into the conjugated polymer by means of chemical or electrochemical oxidation/reduction (a process called doping) following the polymerization reaction. In order to preserve overall electroneutrality of the polymer during introduction of excess charge, ionexhange processes occurs between the polymer phase and the surrounding electrolyte solution. This charge/discharge process can be utilized for application such as; pseudo super capacitors (energy storage through oxidation/reduction processes), electro mechanical actuators (convert electrical energy to mechanical energy) and sensors (converts a chemical signal to electrical conductivity).

In this thesis we describes the synthetic challenges with ECPs for applications vide supra. These mostly relates to solubility, ionic functionalization, conductivity and macromolecular properties such as size and shape of the ECPs. The key requirement in the synthesis of ECPs is that the conjugated nature of the monomer is conserved in the synthesis process and that insertion of excess charge (doping) can be obtained. This limits both the choice of monomer and the choice of polymerization process. Monomers of great complexity have been synthesized with this careful goal in mind. Furthermore, the development of novel monomers must also target the appropriate functionality for polymerization. As such, most ECP monomers are electron-rich molecules with pendant groups containing pyrroles, thiophenes, or 3,4-ethylenedioxythiophenes. These three well known ECP monomers are excellent additions to conjugated systems as they typically enable electrochemical polymerization and direct the polymerizations toward linear polymers with good stability towards doping.

The first topic of this thesis we demonstrate how we can obtain water soluble ECPs with good electrical conductivity by controlling the polymerization techniques and proper ionic functionalization of the monomer. We also show how these polymers can be incorporated by self-assembly with biomolecular templates, such as, DNA and amyloid fibrils, thus generating novel electrically conductive nanowires.

The second topics of this thesis demonstrate how hydrogels of ECPs can be used as bioand charge storage materials, were we demonstrate electronically controlled cell release for biology applications. Both applications are based on ECPs ability to ionexhange processes during electrochemical redox reactions. As well as ions, solvent and other neutral molecules may enter the film during charge/discharge processes. This cause a swelling or shrinking of the ECP films and the expansion and contraction of the polymer network in conjugation with the sorption/desorption of solvent molecules and ions can be described in terms of mechanical work.

In the first case we were able to synthesize a water soluble ECP with high amphiphilic character. The polymer was immobilized onto a flexible electrode, suitable for cell growth and subjected to a cell growth media. When the desired cell layer was formed we applied a potential to the flexible electrode. This resulted in that the mechanical work of the immobilized ECP during the applied potential overcame the week adhesive forces to the flexible electrode, which resulted in super swelling and disintegration of the ICP and the cell layer could be harvested.

In the second case the possibilities of using synthetically modified ECPs as a dopant during electropolymerization of another ECP monomer to obtain a polymer integrated network with high charge density and good charge transport properties. We demonstrate how this polymer network can be used as porous electrodes suitable for supercapacitors.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2012. , 75 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1470
Keyword [en]
Conjugated polyelectrolytes, Electroactive conjugated polyelectrolytes, Intrinsically conducting polyelectrolytes
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-81347ISBN: 978-91-7519-812-5 (print)OAI: oai:DiVA.org:liu-81347DiVA: diva2:551816
Public defence
2012-09-28, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2012-09-12 Created: 2012-09-12 Last updated: 2013-07-01Bibliographically approved
List of papers
1. Iron-Catalyzed Polymerization of Alkoxysulfonate-Functionalized 3,4-Ethylenedioxythiophene Gives Water-Soluble Poly(3,4-ethylenedioxythiophene) of High Conductivity
Open this publication in new window or tab >>Iron-Catalyzed Polymerization of Alkoxysulfonate-Functionalized 3,4-Ethylenedioxythiophene Gives Water-Soluble Poly(3,4-ethylenedioxythiophene) of High Conductivity
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2009 (English)In: Chemistry of Materials, ISSN 0897-4756, E-ISSN 1520-5002, Vol. 21, no 9, 1815-1821 p.Article in journal (Refereed) Published
Abstract [en]

Chemical polymerization of a 3,4-ethylenedioxythiophene derivative bearing a sulfonate group (EDOTS) is reported. The polymer, PEDOT-S, is fully water-soluble and has been produced by polymerizing EDOT-S in water, using Na2S2O8 and a catalytic amount of FeCl3. Elemental analysis and XPS measurements indicate that PEDOT-S is a material with a substantial degree of self-doping, but also contains free sulfate ions as charge-balancing counterions of the oxidized polymer. Apart from self-doping PEDOT-S, the side chains enable full water solubility of the material; DLS studies show an average cluster size of only 2 nm. Importantly, the solvation properties of the PEDOT-S are reflected in spin-coated films, which show a surface roughness of 1.2 nm and good conductivity (12 S/cm) in ambient conditions. The electro-optical properties of this material are shown with cyclic voltammetry and spectroelectrochemical experiment reveals an electrochromic contrast (similar to 48% at lambda(max) = 606 nm).

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2009
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-18398 (URN)10.1021/cm801512r (DOI)000265781000012 ()
Available from: 2009-05-25 Created: 2009-05-25 Last updated: 2014-03-27Bibliographically approved
2. Electrochemical Devices Made from Conducting Nanowire Networks Self-Assembled from Amyloid Fibrils and Alkoxysulfonate PEDOT
Open this publication in new window or tab >>Electrochemical Devices Made from Conducting Nanowire Networks Self-Assembled from Amyloid Fibrils and Alkoxysulfonate PEDOT
2008 (English)In: Nano letters (Print), ISSN 1530-6984, Vol. 8, no 6, 1736-1740 p.Article in journal (Refereed) Published
Abstract [en]

Proteins offer an almost infinite number of functions and geometries for building nanostructures. Here we have focused on amyloid fibrillar proteins as a nanowire template and shown that these fibrils can be coated with the highly conducting polymer alkoxysulfonate PEDOT through molecular self-assembly in water. Transmission electron microscopy and atomic force microscopy show that the coated fibers have a diameter around 15 nm and a length/thickness aspect ratio >1:1000 . We have further shown that networks of the conducting nanowires are electrically and electrochemically active by constructing fully functional electrochemical transistors with nanowire networks, operating at low voltages between 0 and 0.5 V.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-17660 (URN)10.1021/nl0808233 (DOI)
Available from: 2009-04-08 Created: 2009-04-08 Last updated: 2012-09-12
3. Electronic control of cell detachment using a self-doped conducting polymer
Open this publication in new window or tab >>Electronic control of cell detachment using a self-doped conducting polymer
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2011 (English)In: Advanced Materials, ISSN 0935-9648, E-ISSN 1521-4095, Vol. 23, no 38, 4403-4408 p.Article in journal (Refereed) Published
Abstract [en]

An electronic detachment technology based on thin films of a poly(3,4-ethylene-dioxythiophene) derivative is evaluated for controlled release of human epithelial cells. When applying a potential of 1 V, the redox-responsive polymer films detach and disintegrate and at the same time release cells cultured on top in the absence of any enzymatic treatment with excellent preservation of membrane proteins and cell viability.

Place, publisher, year, edition, pages
Wiley-Blackwell, 2011
Keyword
bioelectronics;cell detachment;conducting polymers;electrochemistry;polymerization
National Category
Polymer Chemistry Cell Biology
Identifiers
urn:nbn:se:liu:diva-72170 (URN)10.1002/adma.201101724 (DOI)000297007000009 ()21960476 (PubMedID)
Available from: 2011-11-21 Created: 2011-11-21 Last updated: 2017-12-08
4. Electronic Polymers and DNA Self-assembled in Nanowire Transistors
Open this publication in new window or tab >>Electronic Polymers and DNA Self-assembled in Nanowire Transistors
2013 (English)In: Small, ISSN 1613-6810, E-ISSN 1613-6829, Vol. 9, no 3, 363-368 p.Article in journal (Refereed) Published
Abstract [en]

In this study the fully acidic form of PEDOT-S was used for the purpose of self-assembly onto DNA. We have previously shown that PEDOT-S is a short polymer that is self-doped with !1/3 of the sulfonate side groups acting as the self-doping sites (see supporting info.). The remaining sulfonate groups contribute to a net anionic charge, and a water-soluble polymer, with an intrinsic bulk conductivity of around 30 S/cm. It has been shown that PEDOT-S can bind to oppositely charged cationic amyloid protein structures in water and form conducting nano fibrillar networks, and it has also been shown to form hybrid structures with synthetic peptides, and gold nanoparticles.

Place, publisher, year, edition, pages
Wiley-VCH Verlag Berlin, 2013
Keyword
Organic electronics, conducting polymers, DNA nanotechnology, molecular selfassembly, organic electrochemical transistors
National Category
Natural Sciences Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-81344 (URN)10.1002/smll.201201771 (DOI)000314547200005 ()
Note

Funding Agencies|Strategic Research Foundation SSF through the program OPEN||

Available from: 2012-09-12 Created: 2012-09-12 Last updated: 2017-12-07Bibliographically approved
5. Hydrogels of polypyrrole and self doped PEDOT for porous electrodes and supercapacitors
Open this publication in new window or tab >>Hydrogels of polypyrrole and self doped PEDOT for porous electrodes and supercapacitors
Show others...
2012 (English)Manuscript (preprint) (Other academic)
Abstract [en]

The aim of this work is to extend the knowledge of the mechanism of electropolymerization of pyrrole and PEDOT-S by means of in situ electrochemical quartz microbalance with dissipation studies (EQCM-D), which allow us to evaluate the chemical and physical processes during electrochemical deposition of these conductive polymer composites. Meanwhile, the relationship between the morphology of the films and the mechanism of the electropolymerization of pyrrole in presence of PEDOT-S will be discussed. The resulting material is electroactive, black and conducting. This material is a polymer composite where doped polypyrrole chains are found in an environment of doped PEDOT-S chains. They can be identified through the cyclic voltammetry studies of the composite, through element composition and through their optical signatures in electrochromism. The composite has properties suitable for a supercapacitor electrode, and capacitance of up to 650 F/g has been obtained.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-81346 (URN)
Available from: 2012-09-12 Created: 2012-09-12 Last updated: 2012-09-12Bibliographically approved

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