Cette thèse propose tout d’abord une méthode originale, appelée 2 en 1, de construction contrôlée, couche-par-couche, de films de polyélectrolytes, basée sur le dépôt d’un unique complexe polycation-polyanion. Détaillée dans le cas du poly(éthylènedioxythiophène)-poly(styrènesulfonate) PEDOT-PSS, la méthode est ensuite étendue avec le même succès à d’autres complexes (poly(éthylèneimine) branché-poly(4 styrènesulfonate), poly(diallyldiméthylammonium)-poly(4 styrènesulfonate) et poly(allylamonium)-poly(4 styrènesulfonate)).Les films 2 en 1 de PEDOT PSS sont robustes vis-à-vis d’un recuit thermique et possèdent une conductivité électronique indépendante de leur épaisseur. Cette conductivité peut être améliorée en utilisant un composite contenant des nanoparticules d’or Au Np PEDOT PSS. Des superstructures alternant dépôts de PEDOT PSS et de composite ont, en outre, pu être construites.La construction est contrôlée non seulement sur des substrats rigides (verre, wafer de silicium) mais également sur des substrats élastomère de type silicone (polydiméthylsiloxane PDMS). Le traitement du PDMS par polymérisation plasma d’EDOT sous vide permet le dépôt subséquent de films 2 en 1 de PEDOT PSS. Par ailleurs, la pulvérisation cathodique d’or sur le PDMS permet d’obtenir des conducteurs étirables, de surcroît utilisables comme substrats de films 2 en 1 de PEDOT PSS.Enfin, de nouveaux complexes aqueux synthétisés par voie chimique à partir d’EDOT et d’un polysaccharide (sulfate de chondroïtine A) ont conduit à des films présentant une très bonne conduction qui peut être augmentée par inclusion de nanoparticules d’or. Ces nouveaux composés sont porteurs d’un potentiel très prometteur. / This thesis proposes firstly an original method, called 2 in 1 method, for controlled, layer-by-layer, polyelectrolytes film buildup, based on the deposition of a sole polycation-polyanion complex. Detailed on the case of poly(ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS), the method was then extended with the same success to other complexes (branched poly(ethyleneimine)-poly(4 styrenesulfonate), poly(diallyldimethylammonium)-poly(4 styrenesulfonate) and poly(allylamonium)-poly(4 styrenesulfonate)).The 2 in 1 PEDOT PSS films are robust regarding thermal annealing and have an electronic conductivity independent of their thickness. This conductivity can be improved by using a composite containing gold nanoparticles Au Np PEDOT PSS. Superstructures alternating PEDOT PSS and composite depositions were also obtained.Film buildup is controlled not only on rigid substrates (glass, silicon wafer) but also on elastomeric substrates of the silicon type (polydimethylsiloxane PDMS). The treatment of PDMS by vacuum plasma enhanced chemical vapor deposition (PECVD) of EDOT allows subsequent deposition of 2 in 1 PEDOT-PSS films. Besides, gold sputter deposition on PDMS reaches stretchable conductors. Gold sputtered PDMS can further act as a substrate for 2 in 1 PEDOT-PSS films.Finally, new aqueous complexes, chemically synthesized from EDOT and a polysaccharide (chondroitin sulfate A), lead to films which exhibit a very good conduction, which can be improved by the inclusion of gold nanoparticles. These new complexes are very promising in the field of conductive biomaterials.

Grâce à leurs excellentes propriétés mécaniques, électriques et chimiques, les dispositifs organiques électroniques à base de polymères conducteurs peuvent résoudre l’incompatibilité entre les modules électroniques rigides en silicone et les exigences des tissus mous qui constituent l’environnement biologique. Les avancées en matière de semiconducteurs organiques et en microélectronique ont donné naissance à la bioélectronique. Cette discipline emploie des capteurs à des fins diagnostiques, telles que la détection des métabolites ou la mesure d’un potentiel d’action neuronal, et des actionneurs à des fins thérapeutiques, comme l’application locale d’un traitement à l’intérieur même du corps, ou la stimulation cérébrale profonde afin de guérir un trouble neurologique. En bioélectronique, l’utilisation de matériaux organiques, tels que le polymère conducteur poly(3,4-éthylènedioxythiophène) polystyrène sulfonate de sodium (PEDOT:PSS) a permis de développer des composants électroniques biomédicaux de qualité exceptionnelle, comme par exemple le transistor organique électrochimique (OECT), qui ont été testés in vitro et in vivo. Ce manuscrit explique en détail la fabrication, la fonctionnalisation et la caractérisation du OECT à base de PEDOT:PSS. Afin de pouvoir intégrer ce capteur à des systèmes de mesure biomédicaux déjà établis, l’OECT est intégré à des circuits simples, tels qu’un amplificateur de tension ou un pont de Wheatstone. Ces circuits sont mis à l’épreuve de la pratique clinique, dans le cas de mesures électrocardiographiques, ou de détection de métabolites dans des cellules cancéreuses. Cela permet d’apprécier à la fois leur applicabilité, et leurs limites. / Due to their outstanding mechanical, electrical and chemical properties, organic electronic devices based on conducting polymers can bridge the gap between the rigid silicon based read-out electronics and the soft biological environment and will have a huge impact on the medical healthcare sector. The recent advances in the field of organic semiconductors and microelectronics gave rise to a new discipline termed bioelectronics. This discipline deals with sensors for diagnostic purposes, ranging from metabolite detection and DNA recognition all the way to single neuronal firing events, and actuators for therapeutic purposes, through for example active local drug delivery inside the body or deep brain stimulation to cure neurological disorder. The use of organic materials such as the conducting polymer poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) in the field of bioelectronics has brought about a variety of outstanding electronic biomedical devices, such as the organic electrochemical transistor (OECT), that have been implemented for both in vitro and in vivo applications. The present manuscript gives a detailed explanation of the fabrication, functionalization and characterization of OECTs based on PEDOT:PSS. To be able to intercept this sensor element with traditional biomedical recording systems, the OECT is implemented into simple circuit layouts such as a voltage amplifier or a Wheatstone bridge. These sensor circuits are then applied to real-life biomedical challenges, such as electrocardiographic recordings or metabolite detection in tumor cell cultures, to demonstrate their applicability as well as their limitations.

No description available.

This thesis deals with organic materials and determining their electrical parameters. In the thesis are discussed methods of deposition of organic layers and their measurement. Described are the aspects, which are characteristic for organic materials. They will briefly mention some new components and commercial systems. Special attention is given to conducting polymers and determining their parameters. In the experimental part were measured VA and impedance characteristics of the conductive polymer PEDOT-PSS. The research was also about material degradation in time and effects of thickness on the electrical parameters.

1. Zielstellung der Arbeit war die Entwicklung von Musterkennungsmethoden zur automatischen Klassifizierung von Gasen. Um dieses Ziel zu erreichen, wurde die Reduktionsmethode Parameterabschätzung mittels Adaptive-Simulated-Annealing (ASA-PE) und eine Committee machine (CM) zur Klassifikation entwickelt. 2. Mittels PEDOT:PSS-Sensoren wurden mit Hilfe der Impedanzspektroskopie NH3 und NO2 in unterschiedlichen Konzentrationen gemessen. Die aufgenommenen Messdaten wurden durch die ASA-PE, die Komplexe Haupt-komponentenanalyse (CPCA) und die Discriminant analyses via Support Vector (SVDA) reduziert. 3. Der Vergleich der Merkmalsextraktionsmethoden zeigt: Die in dieser Arbeit neu entwickelte Methode ASA-PE liefert im Vergleich dazu ein sicheres Segmentierungs-Ergebnis. 4. Der Vergleich zwischen ASA-PE und ZView zeigt, dass die ASA-PE eine sichere Methode für die automatisierte Gasanalyse ist. Aber bei zweidimensionalen Merkmalen gibt es einen Bereich, in dem sich eine gemeinsame Häufung einstellt, welche zu einer Irritation in der Auswertung von CPCA und SVDA führen kann. Dieses Problem kann durch eine Erhöhung der Anzahl von Merkmalen gelöst werden. 5. Es wurden sechs die Klassifikationsmethoden: Abstandsgewichtete k-Nächste-Nachbarn-Klassifikation (DW-kNN), das mehrlagige Perzeptron (MLP), Support Vector Machine (SVM), CM, CM ohne MLP und CM mit Abstandskontrolle und AAi-Filter untersucht und miteinander verglichen. Um die Klassifikationsmethoden anzulernen wurden alle Merkmalsreduktions-ergebnisse der CPCA, SVDA und der ASA-PE in Trainings- und Testdaten eingeteilt. 6. Die Ergebnisse zeigen, dass die Kombination aus One-Against-All-SVM (OAA-SVM) und ASA-PE die besten Erkennungsraten liefert. Bei 200 Trainingsdatensätzen wird eine Erkennungsrate von bis zu 99.5% erzielt. Durch diese Kombination können jedoch nur 8 Typen ohne Identifikation von unbekannten Typen ermittelt werden. 7. Wenn das MLP aus CM entfernt wird, werden die Resultate von CM leicht verbessert. Mit Hilfe von 6-Sigma zeigt CM ohne MLP eine gute Erkennungsrate für unbekannte Gase und gleichzeitig bleibt die Erkennungsrate auf einem befriedigenden Niveau. 8. Die Streuung der ASA-PE führt zu einer schlechten Abgrenzung zwischen bekannten und unbekannten Gasen. Stattdessen zeigt die Kombination von CM ohne MLP und CPCA in diesem Fall eine gute Abgrenzung.:Abstract II Danksagung III Inhaltsverzeichnis IV Abkürzungen VII 1 Einführung 1.1 Einleitung 1.2 Entwicklungen bei Gassensoren 1.2.1 Fortschritte bei Material und Messmethode 1.2.2 Fortschritte bei Mustererkennungsmethoden 1.3 Motivation 1.4 Struktur der Arbeit 2 Verfahren zur Gasanalyse 2.1 Messverfahren 2.1.1 Impedanzspektroskopie als Detektionsmethode 2.1.1.1 Definition der Impedanz 2.1.1.2 Bauelemente des elektrischen Modells 2.1.2 Optische Verfahren 2.1.3 Elektrochemische Verfahren 2.2 Merkmalerkennung 2.2.1 Merkmalsreduktion 2.2.1.1 Komplexe Hauptkomponentenanalyse (Engl. Complex Principal Component Analysis) 2.2.1.2 Kernel-Diskriminanzanalyse mittels Support Vektoren (engl. kernel Discriminant Analysis via Support Vector) 2.2.2 Klassifikationsverfahren 2.2.2.1 Abstands-gewichtete k-Nächste-Nachbarn-Klassifikation (engl. Distance weighted k-Nearest-Neighbor-Algorithms, DW-kNN) 2.2.2.2 Mehrlagiges Perzeptron (MLP) 2.2.2.3 Support Vektor Maschine (SVM) 3 Eigene Mustererkennungsverfahren 3.1 Parameterschätzung mittels Adaptive-Simulated-Annealing (ASA-PE) 3.1.1 Allgemeines Impedanzspektroskopiemodell eines Gassensors 3.1.2 Parameterschätzung 3.1.3 Die Optimierungsverfahren 3.2 Committee machine 4 Anwendungsbeispiel 4.1 Experiment mit einem Gassensor aus PEDOT:PSS 4.1.1 Sensoraufbau und vereinfachtes Sensormodell 4.2 Experimentelle Ergebnisse 4.2.1 Messaufbau und Versuchsdurchführung 4.2.2 Vorbereitung zur Messung 4.2.3 Durchführung der Messung 4.2.4 Fehlerbetrachtung 4.2.5 Messergebnisse des Gassensors 4.3 Ergebnisse der Merkmalreduktion 4.3.1 CPCA und SVDA 4.3.2 Parameterschätzung mittels Adaptive-Simulated-Annealing (ASA-PE) 4.4 Ergebnisse der Klassifikationen 4.4.1 Ergebnisse der Gasbestimmung mittels Trainingssatz und Testsatz 4.4.1.1 DW-kNN 4.4.1.2 MLP 4.4.1.3 OAO-SVM 4.4.1.4 OAA-SVM 4.4.1.5 Committee machine 4.4.1.6 CM ohne MLP 4.4.1.7 CM mit AAi-Filter 4.4.2 Abhängigkeit der Klassifikationsergebnisse von der Anzahl der Trainingsdaten 5 Zusammenfassung und Ausblick 5.1 Zusammenfassung 5.2 Ausblick Abbildungsverzeichnis Formelverzeichnis Literaturverzeichnis

[ES] En este trabajo se estudiarán y fabricarán electrodos y sensores depositados mediante diferentes técnicas de impresión sobre sustratos flexibles. En la primera parte se desarrollarán y se comprobará el funcionamiento de electrodos concéntricos tanto bipolares como tripolares para la captación de las señales de la actividad eléctrica del corazón humano. Se probarán tres tipos de deposición de tintas como son el huecograbado, la serigrafía y la inyección de tinta. Las tintas empleadas serán conductoras a base de plata (Ag) y grafito (C) como semiconductoras a base de polímeros orgánicos como el PEDOT-PSS. En otro capítulo se desarrollará y comprobará el funcionamiento de un "touch pad" realizado sobre sustratos textiles, también se desarrollará y comprobará el funcionamiento de un sensor gestual 3D implementado sobre sustrato textiles. Se analizarán la influencia los diferentes elementos constructivos sobre los sensores hápticos capacitivos implementados sobre sustratos textiles. Se analizarán distintas telas con diferentes tratamientos, midiendo las características eléctricas y su iteración con tintas conductoras (Ag) y tintas con polímeros orgánicos semiconductores y aislantes (dieléctricos). Finalmente se utilizará una tinta polimérica semiconductora a base de PEDOT-PSS para la realización de sensores resistivos de humedad y temperatura. Dicha tinta se probará en distintos sustratos, tanto flexibles (textiles y film plástico) como rígidos (alúmina). / [CA] En aquest treball s'estudiaran i fabricaran elèctrodes i sensors dipositats mitjançant tècniques d'impressió diferents sobre substrats flexibles. A la primera part es desenvoluparan i es comprovarà el funcionament d'elèctrodes concèntrics tant bipolars com tripolars per a la captació dels senyals de l'activitat elèctrica del cor humà. Es provaran tres tipus de deposició de tintes com són el gravat al buit, la serigrafia i la injecció de tinta. Les tintes emprades seran conductores a base de plata (Ag) i grafit (C) com a semiconductores a base de polímers orgànics com el PEDOT-PSS. A un altre capítol es desenvoluparà i comprovarà el funcionament d'un "touch pad" realitzat sobre substrats tèxtils, també es desenvoluparà i comprovarà el funcionament d'un sensor gestual 3D implementat sobre substrats tèxtils. S'analitzaran la influència dels diferents elements constructius sobre els sensors hàptics capacitius implementats sobre substrats tèxtils. S'analitzaran diferents teles amb diferents tractaments, mesurant les característiques elèctriques i la seva iteració amb tintes conductores (Ag) i tintes amb polímers orgànics semiconductors i aïllants (dielèctrics). Finalment, s'utilitzarà una tinta polimèrica semiconductor a base de PEDOT-PSS per a la realització de sensors resistius d'humitat i temperatura. Aquesta tinta es provarà en diferents substrats, tant flexibles (tèxtils i film plàstic) com a rígids (alúmina). / [EN] In this work, electrodes and sensors deposited by different printing techniques on flexible substrates will be studied and manufactured. In the first part, the operation of both bipolar and tripolar concentric electrodes for capturing the signals of the electrical activity of the human heart will be developed and tested. Three types of ink deposition will be tested, such as gravure, screen printing and inkjet. The inks used will be conductive based on silver (Ag) and graphite (C) as semiconductor based on organic polymers such as PEDOT-PSS. In another chapter, the operation of a touch pad made on textile substrates will be developed and verified, and the operation of a 3D gesture sensor implemented on textile substrates will also be developed and verified. The influence of the different constructive elements on the capacitive haptic sensors implemented on textile substrates will be analyzed. Different fabrics with different treatments will be analyzed, measuring the electrical characteristics and their iteration with conductive inks (Ag) and inks with semiconductor and insulating organic polymers (dielectric). Finally, a semiconductor polymeric ink based on PEDOT-PSS will be used for the realization of resistive humidity and temperature sensors. This ink will be tested on different substrates, both flexible (textiles and plastic film) and rigid (alumina). / Lidón Roger, JV. (2022). Estudio, desarrollo e implementación de sensores y actuadores realizados con tintes poliméricos sobre substratos flexibles mediante diferentes técnicas de deposición [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/187446

The Thesis reports charge transport studies on conducting polymers, polymer carbon nanotube composites and organic semiconductor devices. Conducting and semiconducting polymers consisting of π-conjugated chains have attracted considerable attention as they combine the optoelectronic properties of semiconductors with mechanical properties and processing advantages of plastics. The chemical/electrochemical/photodoping of these semiconducting polymers can tune the Fermi levels and conductivity in a controlled way, and hence the properties of devices can be easily tailored to suit in several applications. Carbon nanotube (CNT) is another another novel promising material for electronic/optoelectronic applications. Lately there has been a great interest in developing composites of polymer and CNTs to utilize the advantages of both CNTs and polymers. The inclusion of CNTs in polymers improves the mechanical, electrical and thermal properties since the aspect ratio (ratio of length to diameter) is very large, as well its density is rather low. The Thesis consists of 6 chapters. First chapter is a brief introduction of general and transport properties of conducting polymers and polymer-carbon nanotube composites. In Chapter 2, the sample preparation and experimental techniques used in this work are discussed. The charge transport in poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) is presented in Chapter 3. Chapter 4 focuses on the transport measurements in the polymer-CNT composite samples. Chapter 5 elaborates the ac and dc characterization of organic field-effect transistors (OFETs). And chapter 6 presents the conclusion and future directions of the work that has been presented in the Thesis. Chapter 1: In the scientific and technological revolution of the last few years, the study of high performance materials has been steadily increasing including the study of carbon-based materials. Conducting polymers have special properties that are interesting for this new technology. The charge transport in conjugated polymers is important to optimize the performance of devices. The discovery of CNTs with exceptional thermal, mechanical, optical, electrical and structural properties has facilitated the synthesis of new type of nanocomposites with very interesting properties. Nanocomposites represent a guest-host matrix consisting of easily processible functionalized conjugated polymer as host, incorporating CNTs as fillers with versatile electronic and magnetic properties, which provide a wide range of technological applications. To optimize their electrical properties it is essential to understand the charge transport mechanism in detail. Chapter 2: The multi-wall carbon nanotubes (MWNTs) grown by thermal chemical vapor deposition (CVD) are mixed with a 1:1 mixture of 98% H2SO4 and 70% HNO3 to produce sulfonic acid functionalized multi-wall carbon nanotubes (s-MWNTs). The s-MWNTs are dispersed in a solution of Nafion by ultrasonication and then cast on a glass substrate and slowly dried by moderate heating to obtain the composite films. Polyaniline (PANI)-MWNT composites were obtained by carrying out the chemical synthesis of nanofibrilar PANI in the presence of CNTs. This water dispersible PANIMWNT composite contains well segregated MWNTs partially coated by nanofibrilar PANI. The ac and dc charge transport measurements suggest hopping transport in these materials. OFETs are fabricated with pentacene, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene)(PBTTT) and poly(3-hexylthiophene) (P3HT) as active materials. A novel technique is used to characterize the acphotoresponse of these OFETs. Chapter 3: Charge transport studies on PEDOT-PSS have been carried out and found that it correlates with the morphology. The dc conductivity of PEDOT–PSS shows enhanced delocalization of the carriers upon the addition of dimethyl sulfoxide (DMSO) and this is attributed to the extended chain conformation. PEDOT-PSS is known to form a phase-segregated material comprising highly conducting PEDOT grains that are surrounded by a sea of weakly ionic-conducting PSS and a wide variation in the charge transport properties of PEDOT-PSS films is attributed to the degree of phasesegregation of the excess insulating polyanion. The magnetotransport and temperature dependent ac transport parameters across different conducting grades of PEDOT-PSS processed with DMSO were compared. Depending on the subtle alterations in morphology, the transport at low temperatures is shown to vary from the hopping regime (Baytron P) to critical regime of the metal-insulator transition (Baytron PH510) There is a significant positive magnetoresistance (MR) for P–films, but this is considerably less in case of PH510-film. From the low temperature ac conductance it is found that the onset frequency for PH510 is nearly temperature independent, whereas in P type it is strongly temperature dependent, again showing the superior transport in PH510. The presence of ‘shorter network connections’ together with a very weak temperature dependence down to ~ 5 K, suggest that the limitation on transport in PH510 arises from the connectivity within the PEDOT-rich grain rather than transport via the PSS barriers. Chapter 4: DC and AC charge transport properties of Nafion s-MWNT and PANI-MWNT composites are studied. Such a detailed investigation is required to optimize the correlation among morphology and transport properties in these composites towards applications in field-effect transistors, antistatic coating, electromagnetic shielding, etc. The conductivity in Nafion s-MWNT shows a percolative transport with percolation threshold pc = 0.42 whereas such a sharp percolation is absent in PANI-MWNT composite since the conduction via PANI matrix smears out the onset of rapid increase in conductivity. Three-dimensional variable range hopping (VRH) transport is observed in Nafion s-MWNT composites. The positive and negative MR data on 10 wt. % sample are analyzed by taking into account forward interference mechanism (negative MR) and wave-function shrinkage (positive MR), and the carrier scattering is observed to be in the weak limit. The electric-field dependence, measured to high fields, follows the predictions of hopping transport in high electric-field regime. The ac conductivity in 1 wt. % sample follows a power law: ( )  A s , and s decreases with increasing temperature as expected in the correlated barrier hopping (CBH) model. In general, Mott’s VRH transport is observed in PANI-MWNT samples. It is found that the MWNTs are sparingly adhered with PANI coatings, and this facilitates inter-tube hopping at low temperatures. The negative MR of MWNT-PANI composites suggest that the electronic transport at low temperatures is dominated by MWNT network. AC impedance measurements at low temperatures with different MWNT loading show that ac conductivity become temperature independent as the MWNT content increases. The onset frequency for the increase in conductivity is observed to be strongly dependent on the MWNT weight percentage, and the ac conductivity can be scaled onto a master curve given by  ( )  0[1 k( 0 )s ]. Chapter 5: Organic field-effect transistors (OFETs) based on small molecules and polymers have attracted considerable attention due to their unique advantages, such as low cost of fabrication, ease of processing and mechanical flexibility. Impedance characterization of these devices can identify the circuit elements present in addition to the source-drain (SD) channel, and the bottlenecks in charge transport can be identified. The charge carrier trapping at various interfaces and in the semiconductor can be estimated from the dc and ac impedance measurements under illumination. The equivalent circuit parameters for a pentacene OFET are determined from low frequency impedance measurements in the dark as well as under light illumination. The charge accumulation at organic semiconductor–metal interface and dielectric semiconductor interface is monitored from the response to light as an additional parameter to find out the contributions arising from photovoltaic and photoconductive effects. The shift in threshold voltage is due to the accumulation of photogenerated carriers under SD electrodes and at dielectric–semiconductor interface, and also this dominates the carrier transport. Similar charge trapping is observed in an OFET with PBTTT as the active material. This novel method can be used to differentiate the photophysical phenomena occurring in the bulk from that at the metal-semiconductor interface for the polymer. Chapter 6: The conclusions from the various works presented in the thesis are coherently summarized in this chapter. Thoughts for future directions are also summed up.