The development of a complete thermoelectric generator and its application on a display polarizer film was successfully accomplished in this thesis. A systematic study of the prospective thermoelectric materials, PEDOT:PSS-based and ${ZnON}$, used for the present application is presented. To the best of our knowledge, this is the first exploration of the thermoelectric parameters of ${ZnON}$ reported here. Thin-film deposition of these materials was performed via both solution- and vacuum-based techniques. In addition, certain doping mechanisms were tested in an attempt to further understand the correlation between electrical conductivity and Seebeck coefficient. A maximum power factor of $42{\mu}Wm^{-1}K^{-2}$ was achieved for the PEDOT:PSS-based thin film at room temperature. It was initially doped via 5vol% of DMSO and sequentially treated with ethylene glycol. Specifically, its electrical conductivity displayed a 2-fold increase after EG treatment, reaching a value of about 1632 Scm$^{-1}$. Systematic studies performed on the association between thin-film thickness and its Seebeck coefficient shows a decrease in the latter as the number of multilayers printed increases. Among the different $O_{2}/N_{2}$ ratios that were tested for ${ZnON}$ thin films, a maximum power factor value of 163${\mu}Wm^{-1}K{-2}$ was achieved with the lowest $O_{2}$ flow rate configuration. In contrast to PEDOT:PSS-based thin films, the ${ZnON}$ displayed the opposite effect on the relation of the Seebeck coefficient with respect to thin-film thickness. Furthermore, a heterostructure was also developed by implementing ${ZnO}$ nanowires into the ${ZnON}$ thin film. ${ZnO}$ nanowires have been fabricated through the hydrothermal method on inkjet-printed patterns of zinc acetate dihydrate. It has been demonstrated that with the right inkjet-printing parameters and substrate temperature, ${ZnO}$ nanowires can be effortlessly fabricated in accordance with the desired pattern variations under low temperature and mild conditions. Finally, a complete device of the thermoelectric generator was fabricated using the above materials and a special set-up developed in order to test the device on the polarizer. The power output achieved from a 1-thermoelectric couple under normal backlight illumination and ambient conditions was 23pW. Overall, it is thought that the particular design and proof of concept presented here can be the basis of a prospective energy harvesting scheme via thermoelectrics in future display-based handheld devices.

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Die vorliegende Arbeit handelt von der Erforschung und Entwicklung von gedruckten stromführenden Leitern auf dreidimensionalen Objekten, die mit robotergeführten Inkjet-Druck- und Dosierverfahren hergestellt werden. Im Fokus stehen dabei Forschungen, die von den drucktechnischen Grundlagen bis hin zur Demonstration der Technologie und deren Realisierbarkeit anhand konkreter Anwendungsbeispiele reichen. Dabei wird die Entwicklung eines Roboterversuchsstands und einer Vorgehensweise (Workflow) beschrieben, mit denen es möglich ist, Leiterzüge direkt auf 3D-Objekte zu drucken. Die systematische Untersuchung und Optimierung der Technologie und des Prozesses stellt ein Novum dar und ist von großem Interesse für verschiedene Industriezweige wie der Automobil-, Luftfahrt- und Elektronikindustrie. Im Rahmen grundlegender Experimente werden zunächst die digitalen Drucktechnologien Inkjet und Dispensing hinsichtlich der Applikationsfähigkeit flüssiger Funktionsmaterialien auf geneigten und gekrümmten Oberflächen untersucht. Auf Basis der gewonnenen Daten entwickelte Modelle werden vorgestellt, die es ermöglichen, die Positionierungsgenauigkeit einzelner Tintentropfen in Abhängigkeit des Arbeitsabstands sowie den elektrischen Widerstand dispenster Leiterbahnen in Relation zu den Dosierparametern Bahngeschwindigkeit und Volumenstrom zu bestimmen. Im Bereich des Inkjet-Drucks wurde darüber hinaus der Nachweis erbracht, dass unabhängig von der Druckkopforientierung in alle Raumrichtungen annähernd gleich weit und genau gedruckt werden kann. Des Weiteren wurde das Fließverhalten von Schichten, die auf geneigte Oberflächen gedruckt wurden, untersucht und aufgezeigt, dass der elektrische Widerstand über die Leiterzüge ohne Inline-Nachbehandlung ungleich verteilt ist und eine Inline-Nachbehandlung vorteilhaft ist. Leiterzüge, die mit Dosierverfahren hergestellt werden, wurden zudem hinsichtlich der Strombelastbarkeit untersucht. Unter Berücksichtigung der im Rahmen der Grundlagenversuche gewonnenen Erkenntnisse wurden eine Inkjet-gedruckte Sitzheizung, dispenste Leiterbahnen zur verlustarmen Stromversorgung eines Fensterhebermotors und ein komplexes hybrides Sensorsystem zur Temperaturmessung realisiert. Die Ergebnisse können für die Realisierung von automatisierten robotergeführten Druckprozessen zur Herstellung von dreidimensionalen Schaltungsträgern überführt werden.

Porous, conductive metallic nanostructures are required in several fields, such as energy conversion, low-cost sensors etc. This thesis reports on the development of an electrocatalytically active and conductive membrane for use in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) and fabrication of low-cost substrates for Surface Enhanced Raman Spectroscopy (SERS). One of the main challenges facing large-scale deployment of PEMFCs currently is to fabricate a catalyst layer that minimizes platinum loading, maximizes eletrocatalytically active area, and maximizes tolerance to CO in the feed stream. Modeling the kinetics of platinum catalyzed half cell reactions occurring in a PEMFC using the kinetic theory of gases and incorporating appropriate sticking coefficients provides a revealing insight that there is scope for an order of magnitude increase in maximum current density achievable from PEMFCs. To accomplish this, losses due to concentration polarization in gas diffusion layers, which occur at high current densities, need to be eliminated. A novel catalyst design, based on a porous metallic nanostructure, which aims to overcome the limitations of concentration polarization as well as minimize the amount of platinum loading in PEMFCs is proposed. Fabrication steps involving controlled in-plane fusion of self-assembled arrays of core-shell gold-platinum nanoparticles (Au@Pt) is envisioned. The key steps involved being the development of a facile synthesis route to form Au@Pt nanoparticles with tunable platinum shell thicknesses in the 5 nm size range, the formation of large-scale 2D arrays of Au@Pt nanoparticles using guided self-assembly, and optimization of an RF plasma process to promote in-plane fusion of the nanoparticles to form porous, electrocatalytically active and electrically conductive membranes. This thesis consists of seven chapters. The first chapter provides an introduction into the topic of PEMFCs, some perspective on the current status of research and development of PEMFCs, and an outline of the thesis. The second chapter provides an overview on the methods used, characterization techniques employed and protocols followed for sample preparation. The third chapter describes the modelling of a PEMFC using the Kinetic theory of gases to arrive at an estimate of the maximum feasible current density, based on the kinetics of the electrocatalytic reactions. The fourth chapter presents the development of a simple protocol for synthesizing Au@Pt nanoparticles with control over platinum shell thicknesses from the sub monolayer coverage onwards. The results of spectroscopic and microscopic characterization establish the uniformity of coating and the absence of secondary nucleation. Chapter five describes the formation of a nanoporous, electrocatalytically active membrane by self-assembly to form bilayers of 2D arrays of Au@Pt nanoparticles and subsequent fusion using an RF plasma based process. The evolution of the electrocatalytic activity and electrical conductivity as a function of the duration of RF plasma treatment is monitored for Au@Pt nanoparticles with various extent of platinum coating. Spectroscopic, microscopic, electrical and cyclic voltammetry characterization of the samples at various stages were used to understand the structural evolution with RF plasma treatment duration and discussed. Next durability studies were carried out on the nanoporous, Au@Pt bilayer nanoparticle array with an optimum composition of Pt/Au atomic ratio of 0.88 treated to 16 minutes of argon plasma exposure. After this the novel catalyst membrane design of PEM fuel cell is revisited. Two different techniques are proposed so that the thin, nanoporous, metallic catalyst membrane achieves horizontal electronic resistance equivalent to that of the conventional gas diffusion layer with catalyst layer. The first technique proposes the introduction of gold coated polymeric mesh in between the thin, nanoporous, metallic catalyst membrane and bipolar plate and discusses the advantages. Later the gold coated polymeric mesh is introduced in a conventional membrane electrode assembly and efficiency of the polarization curves probed with and without the introduction of gold coated polymeric mesh. The second technique describes the results of fabrication of a nanoporous metallic membrane using multiple layers of 2D Au@Pt nanoparticle arrays at an optimum composition of Pt/Au atomic ratio of 0.88 to reduce the horizontal electronic resistance. Preliminary studies on the permeability of water through such membranes supported on a porous polycarbonate filter membrane are also presented. In chapter six, a simple reactive inkjet printing process for fabricating SERS active silver nanostructures on paper is presented. The process adapts a simple room temperature protocol, using tannic acid as the reducing agent, developed earlier in our group to fabricate porous silver nanostructures on paper using a commercial office inkjet printer. The results of SERS characterization, spectroscopic and microscopic characterizations of the samples and the comparison of the substrate’s long-term performance with respect to a substrate fabricated using sodium borohydride as the reducing agent is discussed. Preliminary findings on attempts to fabricate a conductive silver network using RF plasma induced fusion area also presented. Chapter seven provides a summary of the results, draws conclusions and a perspective on work required to accomplish the goals of incorporating the porous metallic nanostructures into PEMFCs.