Ausgehend von der Anwendung von Folienhinterspritzprozessen für dekorative Zwecke wurde deren Nutzung für die Integration elektronischer Strukturen in Kunststoffbauteile untersucht. Die Herstellung der elektronischen Bauelemente erfolgte mittels verschiedener Druckverfahren mit elektrisch leitfähigen und dielektrischen Materialien auf Polycarbonatfolien. Im Fokus standen zum einen kapazitiv auslesbare Speicherstrukturen und zum anderen Elektrolumineszenzleuchten. Nach dem Druck wurden die bedruckten Folien z. T. verformt und hinterspritzt. In der Arbeit wird auf die Auswirkungen der Verform- und Hinterspritzprozesse eingegangen. Schwerpunktmäßig wird die elektronische bzw. optische Funktionalität der Bauelemente, die Beeinflussung durch Klimaveränderungen und die Haftfestigkeit der Folien betrachtet. Im Ergebnis konnten erstmals die Realisierbarkeit hinterspritzter elektronischer Bauelemente nachgewiesen sowie verschiedene Einflussfaktoren auf deren Funktionalität identifiziert werden. / Based on the application of film insert molding for graphic purposes, the utilization of this process for the integration of electronic devices into plastic components was examined. The manufacturing of the electronic devices was realized by applying electrical conductive and dielectric inks on polycarbonate foil by various printing processes. Capacitive data storage patterns and electroluminescent lamps are the main applications. The production sequence included the printing process, forming of the foil where required and back injection molding. The impact of forming and film insert molding was investigated. The electronic and/or optical functionality of the devices, the influence of ambient conditions like temperature or humidity and the adhesion strength of the foils were in the focus of the evaluation. As a result, the feasibility of film insert molded electronic devices could be verified and various impact factors could be identified for the first time.

With the advancements in the field of wireless sensor networks (WSNs), more and more applications require the sensor nodes to have long lifetime. Energy harvesting sources, e.g. thermoelectric generators (TEGs), can be used to increase the lifetime and capability of the WSNs. Integration of energy harvesters into sensor nodes of WSNs can realize self powered systems, providing the possibility for maintenance free WSNs. TEGs can convert the existing temperature differences into electricity. The efficiency of TEGs is directly related to the dimensionless figure of merit (ZT) of materials, which is given as ZT=σS^2 T/k, where σ is the electrical conductivity, S is the Seebeck coefficient, k is the thermal conductivity, T is the temperature and σS^2 is the power factor. Traditional thermoelectric (TE) materials are based on inorganic materials, of which the thermal conductivity is high. Over the past decade, the use of nanostructuring technology, e.g. superlattice, could decrease the thermal conductivity in order to enhance the efficiency of TE materials. However, the high cost and the rigidity of inorganic TE materials are limiting factors. As alternatives, polymer based materials have become the research focus due to their intrinsic low thermal conductivity, high flexibility and high electrical conductivity. Moreover, polymer based materials could be fabricated in solution form, giving the possibility for employing printing techniques hence a decrease in the production cost. Unlike the typical approach, in which secondary dopants are added into PEDOT:PSS solutions to modify the power factor of polymer films, this thesis is focused on a more efficient method to improve TE properties. This thesis demonstrates for the first time that post treatment of PEDOT:PSS films with the secondary dopant DMSO as the medium results in a much larger power factor than the traditional addition method. The post treatment method also avoids the usually required mixing step involved in the addition method. Different solvents were selected to discuss the impact factors in the modification of the power factor by this post treatment approach. The post treatment of PEDOT:PSS films was then extended to utilize a green solvent EMIMBF_4 (an ionic liquid) as the medium. EMIMBF_4 is found to exchange ions with PEDOT:PSS films. As a result, the EMIM^+ cations remain in the films and reduce the oxidation level of PEDOT chains, which affects the Seebeck coefficient and the electrical conductivity. Furthermore, TE materials based on hybrid composites with polymer as the matrix and Te nanostructures as the nanoinclusions were investigated. This thesis successfully developed a green synthesis method to obtain Te nanostructures, in which a non toxic reductant and a non toxic Te sources were used. Well controlled Te nanostructures including nanorods, nanowires and nanotubes were synthesized by wet chemical and hydrothermal synthesis. Those as synthesized Te nanowires were then integrated into PEDOT:PSS solution for composite films fabrication. A high Seebeck coefficient up to 200 μV/K was observed in the composite film. / Mit den Weiterentwicklungen der Drahtlosen Sensornetzwerke (engl. WSN, wireless sensor networks) stellen immer mehr Anwendungen die Forderung einer langen Lebensdauer der Sensorknoten. Energiegewinnungssysteme (engl. Energy Harvesters) wie z.B. thermoelektrische Generatoren (TEGs) können genutzt werden, um die Lebensdauer und Leistungsfähigkeit der WSN zu steigern. Mit der Integration von Energy Harvesters können WSN ohne äußere Stromversorgung realisiert und somit die Möglichkeit zur Wartungsfreiheit geschaffen werden. TEGs liefern Energie durch die Umwandlung einer Temperaturdifferenz in Elektrizität. Die Effektivität der TEG ist direkt verbunden mit der Material-Kennzahl ZT und ist gegeben durch ZT=σS^2 T/k, wobei σ die elektrische Leitfähigkeit ist, S der Seebeck Koeffizient, k die thermische Leifähigkeit, T die Temperatur und σS^2 der Leistungsfaktor. Herkömmliche thermoelektrische (TE) Materialien basieren auf anorganischen Materialien, von denen die thermische Leitfähigkeit hoch ist. Im Laufe des letzten Jahrzehnts konnte durch den Einsatz der Nanostrukturierung die thermische Leitfähigkeit verringern werden um damit die Effizienz von TE-Materialien zu steigern. Die Steifigkeit dieser Materialien ist ein anderer Aspekt. Als Alternative für anorganische TE Materialien sind Polymer basierte TE Materialien zum Fokus der Forschung geworden aufgrund einer intrinsisch niedrigen thermischen Leitfähigkeit, hohen Flexibilität und hohen elektrischen Leitfähigkeit. Des Weiteren können diese Polymere in gelöster Form verarbeitet werden, was die Möglichkeit für den Einsatz von Drucktechnologien und damit geringeren Produktionskosten gibt. Anders als der herkömmliche Ansatz den Leistungsfaktor der Polymerfilme durch die Ergänzung von sekundären Dotanten in PEDOT:PSS Lösungen zu verändern, wurde in dieser Arbeit eine effizientere Methode zur Verbesserung der TE Eigenschaften gesucht. In dieser Arbeit wird zum ersten Mal gezeigt, dass die Nachbehandlung von PEDOT:PSS Schichten mit sekundären Dotanten Dimethylsulfoxid (DMSO) als Medium der Nachbehandlung zu einem viel höheren Leistungsfaktor führt als bei der Zugabemethode und außerdem die sonst erforderliche Mischprocedur vermeidet. Es wurden verschiedene Lösungsmittel ausgewählt um die Einflussfaktoren bei der Modifikation des Leistungsfaktors durch die Nachbehandlung von Polymerschichten zu diskutieren. Die Nachbehandlung von PEDOT:PSS Schichten wurde nachfolgend erweitert um das umweltfreundliche Lösungsmittel EMIMBF4 (eine ionische Flüssigkeit) als das Medium einzusetzen. EMIMBF4 ist bekannt für den Austausch von Ionen mit PEDOT:PSS Schichten, so dass EMIM Kationen in der Schicht verbleiben, die Oxidationsstufe der PEDOT-Ketten senken und damit den Seebeck-Koeffizient und die elektrische Leitfähigkeit beeinflussen. Des Weiteren konzentriert sich diese Arbeit auf TE Materialien basierend auf Kompositen aus Polymeren mit Nanoeinlagerungen. Erfolgreiche Syntheseansätze wurden für Tellur-Nanostrukturen entwickelt, bei denen keine giftigen Reduktionsmittel und keine giftigen Tellur-Quellen zur Verwendung kamen. Es erfolgte die Erzeugung von kontrollierten Tellur-Nanostrukturen, einschließlich Nanostäben, Nanodrähten und Nanoröhren, mit nass-chemischer und hydrothermaler Synthese. Die so hergestellten Nanodrähte wurden dann in PEDOT:PSS Lösungen integriert für die Herstellung von Komposite-Schichten. Dabei konnte ein hoher Seebeck-Koeffizienten, bis zu 200 μV/K, festgestellt werden.

This work demonstrates an approach to develop low-cost, semi-transparent, long-term stable, and efficient organic photovoltaic (OPV) cells and organic light-emitting diodes (OLEDs) using various alternative electrodes such as conductive polymers, doped ZnO, and carbon nanotubes. Such electrodes are regarded as good candidates to replace the conventional indium tin oxide (ITO) electrode, which is expensive, brittle, and limiting the manufacturing of low-cost, flexible organic devices. First, we report long-term stable, efficient ITO-free OPV cells and transparent OLEDs based on poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) electrodes by using a solvent post-treatment or a structure optimization. In addition, a high performance internal light out-coupling system for white OLEDs based on PEDOT:PSS-coated metal oxide nanostructures is developed. Next, we demonstrate highly efficient ITO-free OPV cells and OLEDs with optimized ZnO electrodes doped with alternative non-metallic elements. The organic devices based on the optimized ZnO electrodes show significantly improved efficiencies compared to devices with standard ITO. Finally, we report semi-transparent OPV cells with free-standing carbon nanotube sheets as transparent top electrodes. The resulting OPV cells exhibit very low leakage currents with good long-term stability. In addition, the combination of various kinds of bottom and top electrodes for semi-transparent and ITO-free OPV cells is investigated. These results demonstrate that alternative electrodes-based OPV cells and OLEDs have a promising future for practical applications in efficient, low-cost, flexible and semi-transparent device manufacturing. / Die vorliegende Arbeit demonstriert einen Ansatz zur Verwirklichung von kostengünstigen, semi-transparenten, langzeitstabilen und effizienten Organischen Photovoltaik Zellen (OPV) und Organischen Leuchtdioden (OLEDs) durch die Nutzung innovativer Elektrodensysteme. Dazu werden leitfähige Polymere, dotiertes ZnO und Kohlenstoff-Nanoröhrchen eingesetzt. Diese alternativen Elektrodensysteme sind vielversprechende Kandidaten, um das konventionell genutzte Indium-Zinn-Oxid (ITO), welches aufgrund seines hohen Preises und spröden Materialverhaltens einen stark begrenz Faktor bei der Herstellung von kostengünstigen, flexiblen, organischen Bauelementen darstellt, zu ersetzten. Zunächst werden langzeitstabile, effiziente, ITO-freie Solarzellen und transparente OLEDs auf der Basis von Poly(3,4-ethylene-dioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS) Elektroden beschrieben, welche mit Hilfe einer Lösungsmittel-Nachprozessierung und einer Optimierung der Bauelementstruktur hergestellt wurden. Zusätzlich wurde ein leistungsfähiges, internes Lichtauskopplungs-System für weiße OLEDs, basierend auf PEDOT:PSS-beschichteten Metalloxid-Nanostrukturen, entwickelt. Weiterhin werden hoch effiziente, ITO-freie OPV Zellen und OLEDs vorgestellt, bei denen mit verschiedenen nicht-metallischen Elementen dotierte ZnO Elektroden zur Anwendung kamen. Die optimierten ZnO Elektroden bieten im Vergleich zu unserem Laborstandard ITO eine signifikant verbesserte Effizienz. Abschließend werden semi-transparente OPV Zellen mit freistehenden Kohlenstoff-Nanoröhrchen als transparente Top-Elektrode vorgestellt. Die daraus resultierenden Zellen zeigen sehr niedrige Leckströme und eine zufriedenstellende Stabilität. In diesem Zusammenhang wurde auch verschiedene Kombinationen von Elektrodenmaterialen als Top- und Bottom-Elektrode für semi-transparente, ITO-freie OPV Zellen untersucht. Zusammengefasst bestätigen die Resultate, dass OPV und OLEDs basierend auf alternativen Elektroden vielversprechende Eigenschaften für die praktische Anwendung in der Herstellung von effizienten, kostengünstigen, flexiblen und semi-transparenten Bauelement besitzen.

The main motivation of this thesis is derived from the fact that physics of disordered systems like conjugated polymer has yet not achieved as concrete understanding as ordered and crystalline systems such as inorganic semiconductors. Through the work done in this thesis, several efforts have been made in order to understand basic charge transport (hopping, current injection) phenomena and photo-physical properties (photoluminescence quenching, absorption, photoconductivity) in conjugated polymer and their hybrid composites. The thesis consists of 7 chapters. Chapter 1 discusses the background knowledge and information of the general properties of conjugated polymers, quantum dots and their hybrid nanocomposites. Chapter 2 deals with the sample preparation and experimental techniques used in this thesis. Chapter 3 elaborates the temperature and field dependent anisotropic charge transport in polypyrrole. Chapter 4 presents an idea to probe and correlate disorder and transport properties using impedance and Raman spectroscopy. Chapter 5 mainly talks about the doping level dependent photophysical and electrical properties of poly(3-hexylthiophene). Chapter 6 reveals the charge transport phenomena in hybrid composites of poly(3,4-ethyldioxythiophene):polysterene sulfonate (PEDOT:PSS) and cadmium telluride quantum dots. Chapter 1: Conjugated polymers and their hybrid systems are easily processible and cost effective material having huge scope for advanced materials of the future. Although variable range hopping (VRH) is widely accepted to model charge transport in π-conjugated systems, but at very low temperatures, high fields, high carrier concentrations one need to explore other models. Conjugated polymers are anisotropic intrinsically. Therefore, anisotropic charge transport can provide basic insights about the physics of charge hopping. Quantum dots, and their hybrid nanocomposites with semiconducting polymers receiving a huge attention for light emission and photovoltaic purposes. It is important to learn about the charge injection,barrier heights, etc. in order to achieve efficient hybrid devices. Chapter 2: Synthesis of the samples, both conjugated polymers and quantum dots, and fabrication of hybrid devices is an important and integral part of this thesis. An Electropolymerization technique is used for making polymer samples on conducting substrates. This is quite interesting because one can tune doping level, disorder and thickness simultaneously. Hydrothermal process is adopted to get highly aqua-dispersible quantum dots. Samples are characterized by different techniques like Raman spectroscopy, energy dispersive spectroscopy. Photoluminescence, UV-Vis absorption, transmission electron microscopy and atomic force microscopy are used to explore several properties of the polymer and hybrid nanocomposites. Chapter 3: It is known that conjugated polymers are intrinsically one–dimensional materials. Therefore it is important to learn anisotropic behavior of these complex systems. Hence, a comparison of electronic transport to their morphology has been carried out and role of carrier density and disorder is discussed further. Both in-plane and out-of-plane charge transport is studied in electrochemically deposited polypyrrole on platinum. Strong anisotropy is observed in the system which is correlated to granular morphology. Field dependence of anisotropic conductivity is also explored. Field scaling analysis shows that all field dependent curves of conductance at different temperatures can fall on to single master curve. Glazman – Matveev model is used to describe nonlinear conduction in field dependence and nonlinearity exponent is estimated. Disorder and carrier density along with the morphological structure like length and orientation of polymer chains with stacking arrangement of different layers in PPy films play an important role in governing the anisotropy in transport properties. Chapter 4: Two different techniques, namely impedance and Raman spectroscopies are used to probe disorder and transport properties in the polypyrrole. An effort is made to correlate the transport properties to the morphology by probing disorder via two different spectroscopic techniques. Frequency dependence of both real and imaginary part has shown that disorder and inhomogeneity varies in different PPy devices, which thus affect the transport properties like conductivity and mobility. Mobility values along the thickness direction for each sample reveal the impact of disorder on out-of¬plane geometry. A circuit based on consideration of the distributed relaxation times, is successfully used to obtain the best fit for the Cole–Cole plot of various PPy devices. FWHM of the de-convoluted peaks of Raman spectra is attributed to the change in distribution of the conjugation length in the PPy films. Chapter 5: The main focus of this chapter is the qualitative exploration of different photo-physical and electrical properties of electropolymerized poly(3-hexylthiophene) and their dependence on doping level. Photoluminescence quenching, band edge shifting in absorption spectra, electrochromic effect, significant enhancement in photocurrent at optimum doping level, two relaxation behaviors in reactance spectra and presence of negative capacitance at low frequencies are distinct features which are observed in poly(3-hexylthiophene) in this work. Quenching in photoluminescence intensity is attributed to charge transfer occurring between polymer chains and dopant ions. Two semicircles in the Cole-Cole plots refer to two type of relaxation process occurring in bulk layer and at interface. Frequency response of capacitance at higher bias and lo side of frequency shows a negative capacitance due to the relaxation mechanism associated with the space-charge effect. Chapter 6: Synthesis of quantum dots and fabrication of hybrid devices is one of the catchy parts of this chapter. Huge quenching photoluminescence intensity and very high increment (~ 400 %) in photocurrent clearly depict the charge transfer at molecular level. Temperature dependent current–voltage characteristics show the absence of thermionic emission since the barrier height is more than the thermal energy of the carriers. Further analysis confirms that the charge carrier injection of ITO/PPCdTe3/Al device is controlled by tunneling processes. The hybrid system has shown a peculiar transition from direct tunneling to Fowler–Nordheim tunneling mechanism which is because of the change in shape of the barrier height from trapezoidal to triangular type with increase in applied electric field. Chapter 7: The conclusions of the different works presented in this thesis are coherently summarized in this thesis. Thoughts and prospective for future directions are also summed up.

This diploma thesis is focused on the study of electric and dielectric properties of transistors based on ionic liquids. The measurements were performed on organic electrochemical transistors with a semiconducting channel made of PEDOT:PSS, which were firstly prepared on ITO substrates, later they were printed using 3D print. Ionic liquid NO4 (1-butyl-3-methylimidazolium hydrogensulfate) was used for measuring of the properties. Electrical properties were determined by measuring volt-ampere characteristics, dielectric properties were measured by impedance spectroscopy.

The aim was to develop a sensing platform on the base of organic electrochemical transistor (OECT). The focus was on the preparation of proper electrode system and on optimalization of properties of thin layer of organic semiconductor. As a base, commercial glass substrates with integrated indium-tin oxide electrodes were chosen. Thin layers were prepared from organic semiconductor poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by spin-coating. Four formulations of material were studied. Layers with different thickness were prepared and the dependence of transconductance on the thickness of the layer and ratio of width and length was observed. The degradation of electrode system was solved by galvanic plating with gold. Attention was also paid to modifications to PEDOT: PSS. It has been found that the optimal layer thickness for use in sensors is approximately 150 nm. By reducing the series resistance by using a silver paste, the transconductance of 23 mS was obtained for the Ink 2, for the Ink 3 the transconductance was 44 mS. Sensoric platforms with these transconductances can be used for detection of physiological functions of electrogenic cells, e.g. cardiomyocytes.

This work demonstrates an approach to develop low-cost, semi-transparent, long-term stable, and efficient organic photovoltaic (OPV) cells and organic light-emitting diodes (OLEDs) using various alternative electrodes such as conductive polymers, doped ZnO, and carbon nanotubes. Such electrodes are regarded as good candidates to replace the conventional indium tin oxide (ITO) electrode, which is expensive, brittle, and limiting the manufacturing of low-cost, flexible organic devices. First, we report long-term stable, efficient ITO-free OPV cells and transparent OLEDs based on poly(3,4-ethylene-dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) electrodes by using a solvent post-treatment or a structure optimization. In addition, a high performance internal light out-coupling system for white OLEDs based on PEDOT:PSS-coated metal oxide nanostructures is developed. Next, we demonstrate highly efficient ITO-free OPV cells and OLEDs with optimized ZnO electrodes doped with alternative non-metallic elements. The organic devices based on the optimized ZnO electrodes show significantly improved efficiencies compared to devices with standard ITO. Finally, we report semi-transparent OPV cells with free-standing carbon nanotube sheets as transparent top electrodes. The resulting OPV cells exhibit very low leakage currents with good long-term stability. In addition, the combination of various kinds of bottom and top electrodes for semi-transparent and ITO-free OPV cells is investigated. These results demonstrate that alternative electrodes-based OPV cells and OLEDs have a promising future for practical applications in efficient, low-cost, flexible and semi-transparent device manufacturing. / Die vorliegende Arbeit demonstriert einen Ansatz zur Verwirklichung von kostengünstigen, semi-transparenten, langzeitstabilen und effizienten Organischen Photovoltaik Zellen (OPV) und Organischen Leuchtdioden (OLEDs) durch die Nutzung innovativer Elektrodensysteme. Dazu werden leitfähige Polymere, dotiertes ZnO und Kohlenstoff-Nanoröhrchen eingesetzt. Diese alternativen Elektrodensysteme sind vielversprechende Kandidaten, um das konventionell genutzte Indium-Zinn-Oxid (ITO), welches aufgrund seines hohen Preises und spröden Materialverhaltens einen stark begrenz Faktor bei der Herstellung von kostengünstigen, flexiblen, organischen Bauelementen darstellt, zu ersetzten. Zunächst werden langzeitstabile, effiziente, ITO-freie Solarzellen und transparente OLEDs auf der Basis von Poly(3,4-ethylene-dioxythiophene):Poly(styrenesulfonate) (PEDOT:PSS) Elektroden beschrieben, welche mit Hilfe einer Lösungsmittel-Nachprozessierung und einer Optimierung der Bauelementstruktur hergestellt wurden. Zusätzlich wurde ein leistungsfähiges, internes Lichtauskopplungs-System für weiße OLEDs, basierend auf PEDOT:PSS-beschichteten Metalloxid-Nanostrukturen, entwickelt. Weiterhin werden hoch effiziente, ITO-freie OPV Zellen und OLEDs vorgestellt, bei denen mit verschiedenen nicht-metallischen Elementen dotierte ZnO Elektroden zur Anwendung kamen. Die optimierten ZnO Elektroden bieten im Vergleich zu unserem Laborstandard ITO eine signifikant verbesserte Effizienz. Abschließend werden semi-transparente OPV Zellen mit freistehenden Kohlenstoff-Nanoröhrchen als transparente Top-Elektrode vorgestellt. Die daraus resultierenden Zellen zeigen sehr niedrige Leckströme und eine zufriedenstellende Stabilität. In diesem Zusammenhang wurde auch verschiedene Kombinationen von Elektrodenmaterialen als Top- und Bottom-Elektrode für semi-transparente, ITO-freie OPV Zellen untersucht. Zusammengefasst bestätigen die Resultate, dass OPV und OLEDs basierend auf alternativen Elektroden vielversprechende Eigenschaften für die praktische Anwendung in der Herstellung von effizienten, kostengünstigen, flexiblen und semi-transparenten Bauelement besitzen.

No description available.

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.

[ES] La capacidad de las células madre para proliferar formando distintas células especializadas les otorga la potencialidad de servir de base para terapias efectivas para patologías cuyo tratamiento era inimaginable hasta hace apenas dos décadas. Sin embargo, esta capacidad se encuentra mediada por estímulos fisiológicos, químicos, y eléctricos, específicos y complejos, que dificultan su traslación a la rutina clínica. Por ello, las células madre representan un campo de estudio en el que se invierten amplios esfuerzos por parte de la comunidad científica. En el ámbito de la regeneración nerviosa, para modular su desarrollo y diferenciación el tratamiento farmacológico, la electroestimulación, y la estimulación optogenética son técnicas que están consiguiendo prometedores resultados. Es por ello por lo que en la presente tesis se ha desarrollado un conjunto de sistemas electrónicos para permitir la aplicación combinada de estas técnicas in vitro, con perspectiva a su aplicación in vivo. Hemos diseñado una novedosa tecnología para la liberación eléctricamente controlada de fármacos. Esta tecnología está basada en nanopartículas de sílice mesoporosa y puertas moleculares de bipiridina-heparina. Las puertas moleculares son electroquímicamente reactivas, y encierran los fármacos en el interior de las nanopartículas, liberándolos ante un estímulo eléctrico. Hemos caracterizado esta tecnología, y la hemos validado mediante la liberación controlada de rodamina en cultivos celulares de HeLa. Para la combinación de liberación controlada de fármacos y electroestimulación hemos desarrollado dispositivos que permiten aplicar los estímulos eléctricos de forma configurable desde una interfaz gráfica de usuario. Además, hemos diseñado un módulo de expansión que permite multiplexar las señales eléctricas a diferentes cultivos celulares. Además, hemos diseñado un dispositivo de estimulación optogenética. Este tipo de estimulación consiste en la modificación genética de las células para que sean sensibles a la radiación lumínica de determinada longitud de onda. En el ámbito de la regeneración de tejido mediante células precursoras neurales, es de interés poder inducir ondas de calcio, favoreciendo su diferenciación en neuronas y la formación de circuitos sinápticos. El dispositivo diseñado permite obtener imágenes en tiempo real mediante microscopía confocal de las respuestas transitorias de las células al ser irradiadas. El dispositivo se ha validado irradiando neuronas modificadas con luz pulsada de 100 ms. También hemos diseñado un dispositivo electrónico complementario de medida de irradiancia con el doble fin de permitir la calibración del equipo de irradiancia y medir la irradiancia en tiempo real durante los experimentos in vitro. Los resultados del uso de los bioactuadores en procesos complejos y dinámicos, como la regeneración de tejido nervioso, son limitados en lazo abierto. Uno de los principales aspectos analizados es el desarrollo de biosensores que permitiesen la cuantización de ciertas biomoléculas para ajustar la estimulación suministrada en tiempo real. Por ejemplo, la segregación de serotonina es una respuesta identificada en la elongación de células precursoras neurales, pero hay otras biomoléculas de interés para la implementación de un control en lazo cerrado. Entre las tecnologías en el estado del arte, los biosensores basados en transistores de efecto de campo (FET) funcionalizados con aptámeros son realmente prometedores para esta aplicación. Sin embargo, esta tecnología no permitía la medición simultánea de más de una biomolécula objetivo en un volumen reducido debido a las interferencias entre los distintos FETs, cuyos terminales se encuentran inmersos en la solución. Por ello, hemos desarrollado instrumentación electrónica capaz de medir simultáneamente varios de estos biosensores, y la hemos validado mediante la medición simultánea de pH y la detección preliminar de serotonina y glutamato. / [CA] La capacitat de les cèl·lules mare per a proliferar formant diferents cèl·lules especialitzades els atorga la potencialitat de servir de base per a teràpies efectives per a patologies el tractament de les quals era inimaginable fins fa a penes dues dècades. No obstant això, aquesta capacitat es troba mediada per estímuls fisiològics, químics, i elèctrics, específics i complexos, que dificulten la seua translació a la rutina clínica. Per això, les cèl·lules mare representen un camp d'estudi en el qual s'inverteixen amplis esforços per part de la comunitat científica. En l'àmbit de la regeneració nerviosa, per a modular el seu desenvolupament i diferenciació el tractament farmacològic, l'electroestimulació, i l'estimulació optogenética són tècniques que estan aconseguint prometedors resultats. És per això que en la present tesi s'ha desenvolupat un conjunt de sistemes electrònics per a permetre l'aplicació combinada d'aquestes tècniques in vitro, amb perspectiva a la seua aplicació in vivo. Hem dissenyat una nova tecnologia per a l'alliberament elèctricament controlat de fàrmacs. Aquesta tecnologia està basada en nanopartícules de sílice mesoporosa i portes moleculars de bipiridina-heparina. Les portes moleculars són electroquímicament reactives, i tanquen els fàrmacs a l'interior de les nanopartícules, alliberant-los davant un estímul elèctric. Hem caracteritzat aquesta tecnologia, i l'hem validada mitjançant l'alliberament controlat de rodamina en cultius cel·lulars de HeLa. Per a la combinació d'alliberament controlat de fàrmacs i electroestimulació hem desenvolupat dispositius que permeten aplicar els estímuls elèctrics de manera configurable des d'una interfície gràfica d'usuari. A més, hem dissenyat un mòdul d'expansió que permet multiplexar els senyals elèctrics a diferents cultius cel·lulars. A més, hem dissenyat un dispositiu d'estimulació optogenètica. Aquest tipus d'estimulació consisteix en la modificació genètica de les cèl·lules perquè siguen sensibles a la radiació lumínica de determinada longitud d'ona. En l'àmbit de la regeneració de teixit mitjançant cèl·lules precursores neurals, és d'interés poder induir ones de calci, afavorint la seua diferenciació en neurones i la formació de circuits sinàptics. El dispositiu dissenyat permet obtindré imatges en temps real mitjançant microscòpia confocal de les respostes transitòries de les cèl·lules en ser irradiades. El dispositiu s'ha validat irradiant neurones modificades amb llum polsada de 100 ms. També hem dissenyat un dispositiu electrònic complementari de mesura d'irradiància amb el doble fi de permetre el calibratge de l'equip d'irradiància i mesurar la irradiància en temps real durant els experiments in vitro. Els resultats de l'ús dels bioactuadors en processos complexos i dinàmics, com la regeneració de teixit nerviós, són limitats en llaç obert. Un dels principals aspectes analitzats és el desenvolupament de biosensors que permeteren la quantització de certes biomolècules per a ajustar l'estimulació subministrada en temps real. Per exemple, la segregació de serotonina és una resposta identificada amb l'elongació de les cèl·lules precursores neurals, però hi ha altres biomolècules d'interés per a la implementació d'un control en llaç tancat. Entre les tecnologies en l'estat de l'art, els biosensors basats en transistors d'efecte de camp (FET) funcionalitzats amb aptàmers són realment prometedors per a aquesta aplicació. No obstant això, aquesta tecnologia no permetia el mesurament simultani de més d'una biomolècula objectiu en un volum reduït a causa de les interferències entre els diferents FETs, els terminals dels quals es troben immersos en la solució. Per això, hem desenvolupat instrumentació electrònica capaç de mesurar simultàniament diversos d'aquests biosensors i els hem validat amb mesurament simultani del pH i la detecció preliminar de serotonina i glutamat. / [EN] The stem cells' ability to proliferate to form different specialized cells gives them the potential to serve as the basis for effective therapies for pathologies whose treatment was unimaginable until just two decades ago. However, this capacity is mediated by specific and complex physiological, chemical, and electrical stimuli that complicate their translation to clinical routine. For this reason, stem cells represent a field of study in which the scientific community is investing a great deal of effort. In the field of nerve regeneration, to modulate their development and differentiation, pharmacological treatment, electrostimulation, and optogenetic stimulation are techniques that are achieving promising results. For this reason, we have developed a set of electronic systems to allow the combined application of these techniques in vitro, with a view to their application in vivo. We have designed a novel technology for the electrically controlled release of drugs. This technology is based on mesoporous silica nanoparticles and bipyridine-heparin molecular gates. The molecular gates are electrochemically reactive and entrap the drugs inside the nanoparticles, releasing them upon electrical stimulus. We have characterized this technology and validated it by controlled release of rhodamine in HeLa cell cultures. For combining electrostimulation and controlled drug release we have developed devices that allow applying the different electrical stimuli in a configurable way from a graphical user interface. In addition, we have designed an expansion module that allows multiplexing electrical signals to different cell cultures. In addition, we have designed an optogenetic stimulation device. This type of stimulation consists of genetically modifying cells to make them sensitive to light radiation of a specific wavelength. In tissue regeneration using neural precursor cells, it is interesting to be able to induce calcium waves, favoring the cell differentiation into neurons and the formation of synaptic circuits. The designed device enable the obtention of real-time images through confocal microscopy of the transient responses of cells upon irradiation. The device has been validated by irradiating modified neurons with 100 ms pulsed light stimulation. We have also designed a complementary electronic irradiance measurement device to allow calibration of the irradiator equipment and measuring irradiance in real time during in vitro experiments. The results of using bioactuators in complex and dynamic processes, such as nerve tissue regeneration, are limited in an open loop. One of the main aspects analyzed is the development of biosensors that would allow quantifying of specific biomolecules to adjust the stimulation provided in real time. For instance, serotonin secretion is an identified response of neural precursor cells elongation, among other biomolecules of interest for the implementation of a closed-loop control. Among the state-of-the-art technologies, biosensors based on field effect transistors (FETs) functionalized with aptamers are promising for this application. However, this technology did not allow the simultaneous measurement of more than one target biomolecule in a small volume due to interferences between the different FETs, whose terminals are immersed in the solution. This is why we have developed electronic instrumentation capable of simultaneously measuring several of these biosensors, and we have validated it with the simultaneous pH measurement and the preliminary detection of serotonin and glutamate. / Monreal Trigo, J. (2023). Electronic Devices for the Combination of Electrically Controlled Drug Release, Electrostimulation, and Optogenetic Stimulation for Nerve Tissue Regeneration [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/193841