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Ionic and electronic transport in electrochemical and polymer based systems
Linköping University, Department of Science and Technology, Physics and Electronics. Linköping University, Faculty of Science & Engineering.ORCID iD: 0000-0002-3118-5584
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Electrochemical systems, which rely on coupled phenomena of the chemical change and electricity, have been utilized for development an interface between biological systems and conventional electronics.  The development and detailed understanding of the operation mechanism of such interfaces have a great importance to many fields within life science and conventional electronics. Conducting polymer materials are extensively used as a building block in various applications due to their ability to transduce chemical signal to electrical one and vice versa. The mechanism of the coupling between the mass and charge transfer in electrochemical systems, and particularly in conductive polymer based system, is highly complex and depends on various physical and chemical properties of the materials composing the system of interest.

The aims of this thesis have been to study electrochemical systems including conductive polymer based systems and provide knowledge for future development of the devices, which can operate with both chemical and electrical signals. Within the thesis, we studied the operation mechanism of ion bipolar junction transistor (IBJT), which have been previously utilized to modulate delivery of charged molecules. We analysed the different operation modes of IBJT and transition between them on the basis of detailed concentration and potential profiles provided by the model.

We also performed investigation of capacitive charging in conductive PEDOT:PSS polymer electrode. We demonstrated that capacitive charging of PEDOT:PSS electrode at the cyclic voltammetry, can be understood within a modified Nernst-Planck-Poisson formalism for two phase system in terms of the coupled ion-electron diffusion and migration without invoking the assumption of any redox reactions.

Further, we studied electronic structure and optical properties of a self-doped p-type conducting polymer, which can polymerize itself along the stem of the plants. We performed ab initio calculations for this system in undoped, polaron and bipolaron electronic states. Comparison with experimental data confirmed the formation of undoped or bipolaron states in polymer film depending on applied biases.

Finally, we performed simulation of the reduction-oxidation reaction at microband array electrodes. We showed that faradaic current density at microband array electrodes increases due to non-linear mass transport on the microscale compared to the corresponding macroscale systems.  The studied microband array electrode was used for developing a laccase-based microband biosensor. The biosensor revealed improved analytical performance, and was utilized for in situ phenol detection.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2017. , 49 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1841
Keyword [en]
Modeling, Charge transport, Charge carriers Electrochemical systems, Polymer, PEDOT:PSS, Supercapacitance, Cyclic voltammetry, double layers, Nernst-Planck-Poisson, DFT, TDDFT, Ion Bipolar Junction Transistor, ETE-S
National Category
Materials Chemistry Condensed Matter Physics Inorganic Chemistry Textile, Rubber and Polymeric Materials
Identifiers
URN: urn:nbn:se:liu:diva-135429DOI: 10.3384/diss.diva-1082793ISBN: 9789176855485 (print)OAI: oai:DiVA.org:liu-135429DiVA: diva2:1082793
Public defence
2017-04-25, K3, Kåkenhus, Campus Norrköping, Norrköping, 10:15 (English)
Opponent
Supervisors
Available from: 2017-03-24 Created: 2017-03-17 Last updated: 2017-08-30Bibliographically approved
List of papers
1. Modeling of Charge Transport in Ion Bipolar Junction Transistors
Open this publication in new window or tab >>Modeling of Charge Transport in Ion Bipolar Junction Transistors
2014 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, no 23, 6999-7005 p.Article in journal (Refereed) Published
Abstract [en]

Spatiotemporal control of the complex chemical microenvironment is of great importance to many fields within life science. One way to facilitate such control is to construct delivery circuits, comprising arrays of dispensing outlets, for ions and charged biomolecules based on ionic transistors. This allows for addressability of ionic signals, which opens up for spatiotemporally controlled delivery in a highly complex manner. One class of ionic transistors, the ion bipolar junction transistors (IBJTs), is especially attractive for these applications because these transistors are functional at physiological conditions and have been employed to modulate the delivery of neurotransmitters to regulate signaling in neuronal cells. Further, the first integrated complementary ionic circuits were recently developed on the basis of these ionic transistors. However, a detailed understanding of the device physics of these transistors is still lacking and hampers further development of components and circuits. Here, we report on the modeling of IBJTs using Poissons and Nernst-Planck equations and the finite element method. A two-dimensional model of the device is employed that successfully reproduces the main characteristics of the measurement data. On the basis of the detailed concentration and potential profiles provided by the model, the different modes of operation of the transistor are analyzed as well as the transitions between the different modes. The model correctly predicts the measured threshold voltage, which is explained in terms of membrane potentials. All in all, the results provide the basis for a detailed understanding of IBJT operation. This new knowledge is employed to discuss potential improvements of ion bipolar junction transistors in terms of miniaturization and device parameters.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2014
National Category
Electrical Engineering, Electronic Engineering, Information Engineering Physical Sciences
Identifiers
urn:nbn:se:liu:diva-109131 (URN)10.1021/la404296g (DOI)000337644200044 ()24854432 (PubMedID)
Available from: 2014-08-13 Created: 2014-08-11 Last updated: 2017-03-17Bibliographically approved
2. In vivo polymerization and manufacturing of wires and supercapacitors in plants
Open this publication in new window or tab >>In vivo polymerization and manufacturing of wires and supercapacitors in plants
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2017 (English)In: Proceedings of the National Academy of Sciences of the United States of America, ISSN 0027-8424, E-ISSN 1091-6490, Vol. 114, no 11, 2807-2812 p.Article in journal (Refereed) Published
Abstract [en]

Electronic plants, e-Plants, are an organic bioelectronic platform that allows electronic interfacing with plants. Recently we have demonstrated plants with augmented electronic functionality. Using the vascular system and organs of a plant, we manufactured organic electronic devices and circuits in vivo, leveraging the internal structure and physiology of the plant as the template, and an integral part of the devices. However, this electronic functionality was only achieved in localized regions, whereas new electronic materials that could be distributed to every part of the plant would provide versatility in device and circuit fabrication and create possibilities for new device concepts. Here we report the synthesis of such a conjugated oligomer that can be distributed and form longer oligomers and polymer in every part of the xylem vascular tissue of a Rosa floribunda cutting, forming long-range conducting wires. The plant’s structure acts as a physical template, whereas the plant’s biochemical response mechanism acts as the catalyst for polymerization. In addition, the oligomer can cross through the veins and enter the apoplastic space in the leaves. Finally, using the plant’s natural architecture we manufacture supercapacitors along the stem. Our results are preludes to autonomous energy systems integrated within plants and distribute interconnected sensor-actuator systems for plant control and optimization

Place, publisher, year, edition, pages
National Academy of Sciences, 2017
National Category
Plant Biotechnology Condensed Matter Physics Textile, Rubber and Polymeric Materials Chemical Sciences
Identifiers
urn:nbn:se:liu:diva-135492 (URN)10.1073/pnas.1616456114 (DOI)000396094200029 ()
Note

Funding agencies: Knut and Alice Wallenberg Foundation Scholar Grant [KAW 2012.0302]; Linkoping University; Onnesjo Foundation; Wenner-Gren Foundations; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkping University [SFO-Mat-

Available from: 2017-03-16 Created: 2017-03-16 Last updated: 2017-04-03Bibliographically approved
3. Total phenol analysis of weakly supported water using a laccase-based microband biosensor.
Open this publication in new window or tab >>Total phenol analysis of weakly supported water using a laccase-based microband biosensor.
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2016 (English)In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 907, 45-53 p.Article in journal (Refereed) Published
Abstract [en]

The monitoring of phenolic compounds in wastewaters in a simple manner is of great importance for environmental control. Here, a novel screen printed laccase-based microband array for in situ, total phenol estimation in wastewaters and for water quality monitoring without additional sample pre-treatment is presented. Numerical simulations using the finite element method were utilized for the characterization of micro-scale graphite electrodes. Anodization followed by covalent modification was used for the electrode functionalization with laccase. The functionalization efficiency and the electrochemical performance in direct and catechol-mediated oxygen reduction were studied at the microband laccase electrodes and compared with macro-scale electrode structures. The reduction of the dimensions of the enzyme biosensor, when used under optimized conditions, led to a significant improvement in its analytical characteristics. The elaborated microsensor showed fast responses towards catechol additions to tap water – a weakly supported medium – characterized by a linear range from 0.2 to 10 μM, a sensitivity of 1.35 ± 0.4 A M−1 cm−2 and a dynamic range up to 43 μM. This enhanced laccase-based microsensor was used for water quality monitoring and its performance for total phenol analysis of wastewater samples from different stages of the cleaning process was compared to a standard method.

Place, publisher, year, edition, pages
Elsevier, 2016
Keyword
Laccase; microelectrode; microband; electrochemical modeling; total phenol analysis; wastewater
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:liu:diva-123677 (URN)10.1016/j.aca.2015.12.006 (DOI)000368422900005 ()
Note

Funding agencies: Swedish research council Formas [245-2010-1062]; research centre Security Link [VINNOVA 2009-00966]; Norrkopings fond for Forskning och Utveckling; VINNOVA

Available from: 2016-01-07 Created: 2016-01-07 Last updated: 2017-03-17Bibliographically approved
4. Understanding the Capacitance of PEDOT:PSS
Open this publication in new window or tab >>Understanding the Capacitance of PEDOT:PSS
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2017 (English)In: Advanced Functional Materials, ISSN 1616-301X, E-ISSN 1616-3028, Vol. 27, no 28, 1700329Article in journal (Refereed) Published
Abstract [en]

Poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) is the most studied and explored mixed ion-electron conducting polymer system. PEDOT: PSS is commonly included as an electroactive conductor in various organic devices, e.g., supercapacitors, displays, transistors, and energy-converters. In spite of its long-term use as a material for storage and transport of charges, the fundamentals of its bulk capacitance remain poorly understood. Generally, charge storage in supercapacitors is due to formation of electrical double layers or redox reactions, and it is widely accepted that PEDOT: PSS belongs to the latter category. Herein, experimental evidence and theoretical modeling results are reported that significantly depart from this commonly accepted picture. By applying a two-phase, 2D modeling approach it is demonstrated that the major contribution to the capacitance of the two-phase PEDOT: PSS originates from electrical double layers formed along the interfaces between nanoscaled PEDOT-rich and PSS-rich interconnected grains that comprises two phases of the bulk of PEDOT: PSS. This new insight paves a way for designing materials and devices, based on mixed ion-electron conductors, with improved performance.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2017
Keyword
cyclic voltammetry; double layers; Nernst-Planck-Poisson modeling; PEDOT:PSS; supercapacitance
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:liu:diva-139550 (URN)10.1002/adfm.201700329 (DOI)000406183100003 ()
Note

Funding Agencies|The Swedish Energy Agency [38332-1]; Swedish Research Council [245-2010-1062]; Research Centre Security Link [VINNOVA 2009-00966]; Norrkopings fond for Forskning och Utveckling; CeNano; Knut and Alice Wallenberg Foundation; Swedish Foundation for Strategic Research (SSF); Advanced Functional Material SFO-center at Linkoping University [2009-00971]; Swedish National Infrastructure for Computing (SNIC); European Research Council (ERC) [307596, 681881]; Knut and Alice Wallenberg Foundation (Tail of the Sun); Swedish Foundation for Strategic Research [0-3D]

Available from: 2017-08-08 Created: 2017-08-08 Last updated: 2017-08-30
5. Spectroelectrochemistry and Nature of Charge Carriers in Self-Doped Conducting Polymer
Open this publication in new window or tab >>Spectroelectrochemistry and Nature of Charge Carriers in Self-Doped Conducting Polymer
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2017 (English)In: ADVANCED ELECTRONIC MATERIALS, ISSN 2199-160X, Vol. 3, no 8, 1700096Article in journal (Refereed) Published
Abstract [en]

A recently developed water-soluble self-doped sodium salt of bis[3,4-ethylenedioxythiophene] 3thiophene butyric acid (ETE-S) is electropolymerized and characterized by means of spectroelectrochemistry, electron paramagnetic resonance spectroscopy, and cyclic voltammetry, combined with the density functional theory (DFT) and time-dependent DFT calculations. The focus of the studies is to underline the nature of the charge carriers when the electrochemically polymerized ETE-S films undergo a reversible transition from reduced to electrically conductive oxidized states. Spectroelectrochemistry shows clear distinctions between absorption features from reduced and charged species. In the reduced state, the absorption spectrum of ETE-S electropolymerized film shows a peak that is attributed to HOMO. LUMO transition. As the oxidation level increases, this peak diminishes and the absorption of the film is dominated by spinless bipolaronic states with some admixture of polaronic states possessing a magnetic momentum. For fully oxidized samples, the bipolaronic states fully dominate, and the features in the absorption spectra are related to the drastic changes of the band structure, exhibiting a strong decrease of the band gap when a polymeric film undergoes oxidation.

Place, publisher, year, edition, pages
WILEY, 2017
Keyword
bipolarons; polarons; self-doped conducting polymers; spectroelectrochemistry
National Category
Other Materials Engineering
Identifiers
urn:nbn:se:liu:diva-140056 (URN)10.1002/aelm.201700096 (DOI)000407317700015 ()
Note

Funding Agencies|The Swedish Energy Agency [38332-1]; Norrkopings fond for Forskning och Utveckling, Carl Tryggers Stiftelse for Vetenskaplig Forskning [CTS: 13527]; CeNano (Linkoping University); Knut and Alice Wallenberg foundation (Tail of the Sun); Swedish Foundation for Strategic Research (SSF); Advanced Functional Material SFO-center at the Linkoping University (Faculty Grant SFO-Mat-LiU) [2009-00971]; Marie Sklodowska Curie Individual Fellowship (MSCA-IF-EF-ST); Marie Sklodowska Curie Individual Fellowship (Trans-Plant); Marie Sklodowska Curie Individual Fellowship [702641]

Available from: 2017-08-28 Created: 2017-08-28 Last updated: 2017-09-18

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