Silver nanowire transparent electrodes have recently received much attention as a replacement for indium tin oxide (ITO) for use in various electronic devices such as touch panels, organic solar cells, and displays. The fabrication of silver nanowire electrodes on glass substrates with a sheet resistance as low as 9 Ω/□ and 90% optical transparency at 550 nm is demonstrated. These resistance and transparency values match that of commercially available indium tin oxide and are superior to other alternatives such as carbon nanotube electrodes. The nanowire electrodes are low cost and easy to fabricate. Moreover, by depositing nanowire films on plastic substrates, mechanically flexible electrodes are obtained. The silver nanowire electrodes are integrated into several electronic devices: transparent heaters, organic solar cells, and switchable privacy glass. The concerns about the suitability of silver nanowire electrodes for use in commercial electronic devices are discussed. High surface roughness, one of the major concerns, is addressed by introducing a new method of embedding silver nanowires in a soft polymer. The instability of silver nanowire electrodes under current flow is also demonstrated for the first time. It is shown that silver nanowire electrodes fail under current flow after ass little as 2 days. This failure is caused by Joule heating which causes the nanowires to break up and thus create an electrical discontinuity in the nanowire film. Suggestions for improving the longevity of the electrodes are given.

Silver nanowire transparent electrodes have recently received much attention as a replacement for indium tin oxide (ITO) for use in various electronic devices such as touch panels, organic solar cells, and displays. The fabrication of silver nanowire electrodes on glass substrates with a sheet resistance as low as 9 Ω/□ and 90% optical transparency at 550 nm is demonstrated. These resistance and transparency values match that of commercially available indium tin oxide and are superior to other alternatives such as carbon nanotube electrodes. The nanowire electrodes are low cost and easy to fabricate. Moreover, by depositing nanowire films on plastic substrates, mechanically flexible electrodes are obtained. The silver nanowire electrodes are integrated into several electronic devices: transparent heaters, organic solar cells, and switchable privacy glass. The concerns about the suitability of silver nanowire electrodes for use in commercial electronic devices are discussed. High surface roughness, one of the major concerns, is addressed by introducing a new method of embedding silver nanowires in a soft polymer. The instability of silver nanowire electrodes under current flow is also demonstrated for the first time. It is shown that silver nanowire electrodes fail under current flow after ass little as 2 days. This failure is caused by Joule heating which causes the nanowires to break up and thus create an electrical discontinuity in the nanowire film. Suggestions for improving the longevity of the electrodes are given.

No description available.

Transparent electrodes (TEs) require materials that have both transparency and electrical conductivity, a combination not usually found in nature. They are in increasing demand for use in solar cells, touch screens, displays, transparent heating films and several other devices. Most TEs used today are made of indium tin oxide (ITO). However, it has several disadvantages, such as high fabrication cost, rigidity and brittleness. Many ITO alternatives are being pursued, among which metallic nanowire (NW) networks on transparent substrates such as glass or polymer, have received much attention. This thesis demonstrates ordered silver NW networks on polyimide, fabricated by the field-directed chaining technique. We achieved a sheet resistance of 27 Ω/sq and 95.4% transparency at 550nm, with a Figure of Merit (FOM) 0.023Ω-1, which is higher than the FOM of commercial ITO, 0.005Ω-1. We have demonstrated that ordered NW networks, directed by alternative current (AC) electric fields, are easy to fabricate over a large area and at low cost, on rigid and flexible substrates. The AC electric field changes with different experiment setup. In this work, the effect of polymer thickness, electric field frequency, and gap size between electrodes are explored by COMSOL simulation and validated experimentally. By choosing the appropriate frequency and gap size, ordered NW networks are successfully created on a 23μm polyethylene terephthalate (PET) sheet. Fluid motion is one of the disruptors during NW chaining. We demonstrate control of this disruptor by the use of sandwiched channels for the NW suspension. Post-fabrication treatments are important and necessary for improving the connectivity and conductivity of Ag NW networks. In this work, we explore Joule heating and show its potential to improve the conductivity over other post-treatment approaches. However, Joule heating can also cause failures of NW networks. Ordered NW networks present better optical-electrical properties than random NW networks. Post-fabrication treatment can improve the properties, but there is a limit. In this work, a mathematical model is built for optical-electrical properties of perfectly ordered NW networks, which sets the upper bound of performance for transparent electrodes made of NW networks. A linear relationship is found between the transmittance and inverse sheet resistance. The model is then modified with factors to account for departure from the ideal. / Graduate / 2019-12-12

No description available.

The aim of this work was to investigate silver nanowire as well as carbon nanotube networks as transparent conducting electrodes for small molecule organic solar cells. In the framework of the nanowire investigations, a low-temperature method at less than 80 °C is developed to obtain highly conductive networks directly after the deposition and without post-processing. In detail, specific non-conductive organic materials act as a matrix where the nanowires are embedded in such that a mutual attraction based on capillary forces and hydrophobic interaction is created. This process is mediated by the ethanol contained in the nanowire dispersion and works only for sublayer materials which exhibit hydrophobic and hydrophilic groups at the same time. In contrast to high-temperature processed reference electrodes (210 °C for 90 min) without matrix, a slightly lower sheet resistance of 10.8 Ohm/sq at a transparency of 80.4 % (including substrate) is obtained by using polyvinylpyrrolidone as the sublayer material. In comparison to annealed silver nanowire networks, the novel approach yields a performance enhancement in corresponding organic solar cells which can compete with ITO-based devices. Furthermore, a novel approach for scalable, highly conductive, and transparent silver nanowire top-electrodes for organic optoelectronic devices is introduced. By utilizing a perfluorinated methacrylate as stabilizer, silver nanowires with high aspect ratio can be transferred into inert solvents which do not dissolve most organic compounds making this modified dispersion compatible with small molecule and polymer-based organic optoelectronic devices. The inert silver nanowire dispersion yields highly performing top-electrodes with a sheet resistance of 10.0 Ohm/sq at 80.0 % transparency (including substrate) directly after low-temperature deposition at 30 °C and without further post-processing. In comparison to similarly prepared reference devices comprising a thin-metal film as transparent top-electrode, reasonable power conversion efficiencies are demonstrated by spray-coating this dispersion directly on simple, air-exposed small molecule-based organic solar cells. Moreover, a deeper understanding of the percolation behavior of silver nanowire networks has been achieved. Herein, direct measurements of the basic network parameters, including the wire-to-wire junction resistance and the resistance of a single nanowire of pristine and annealed networks have been carried out for the first time. By putting the values into a simulation routine, a good accordance between measurement and simulation is achieved. Thus, an examination of the electrical limit of the nanowire system used in this work can be realized by extrapolating the junction resistance down to zero. The annealed silver nanowires are fairly close to the limit with a theoretical enhancement range of only 20 % (common absolute sheet resistance of approximately 10 Ohm/sq) such that a significant performance improvement is only expected by an enlargement of the nanowire length or by the implementation of new network geometries. In addition, carbon nanotube networks are investigated as alternative network-type, transparent bottom-electrode for organic small molecule solar cells. For that purpose, cleaning and structuring as well as planarization procedures are developed and optimized which maintain the optoelectronic performance of the carbon nanotube electrodes. Furthermore, a hybrid electrode consisting of silver nanowires covered with carbon nanotubes is fabricated yielding organic solar cells with only 0.47 % power conversion efficiency. In contrast, optimized electrodes comprising only carbon nanotubes show significantly higher efficiency. In comparison to identically prepared ITO devices, comparable or lower power conversion efficiencies of 3.96 % (in p-i-n stack), 4.83 % (in cascade cell) as well as 4.81 % (in p-n-i-p architecture) are demonstrated. For an inverted n-i-p stack design, the highest power conversion efficiency of 5.42 % is achieved.

In dieser Arbeit wurden einerseits die elektronischen Eigenschaften von Graphenen und andererseits die Verwendung von Graphenen und Kohlenstoff-basierten Hybridmaterialien als transparente Elektroden untersucht. Entsprechend ist der erste, umfangreichere Teil der Arbeit Grundlagen-orientiert und fokussiert auf die elektrostatische Wechselwirkung zwischen Graphen und dem Substrat Glimmer. Der zweite, kleinere Teil befasst sich mit der Entwicklung leitfähiger Tinten auf der Basis von Graphenen und anderen Kohlenstoff-basierten Hybridmaterialien für Anwendungen in der druckbaren Elektronik, insbesondere für die Herstellung transparenter Elektroden. Graphen auf Glimmer ist ein sehr wohldefiniertes System, in dem das Graphen über mehrere Quadratmikrometer atomar flach ist. Schichtdickenabhängige Variationen des Oberflächenpotentials von einzel- und mehrlagigen Graphenen auf Glimmer wurden mittels Kelvin Probe Rasterkraftmikroskopie untersucht. Damit konnte die elektrostatische Abschirmlänge von Graphen auf Glimmer bestimmt werden. Lokale Variationen des Oberflächenpotentials innerhalb einer Graphenlage, verursacht durch eingeschlossene Wasserschichten zwischen Graphen und Glimmer, wurden mit Rasterkraftmikroskopie, elektrostatischer Rasterkraftmikroskopie und der Raman-Spektroskopie untersucht. Dies ermöglichte es, die Dotierung von Graphen durch eingeschlossene Wasserschichten zu quantifizieren. Außerdem wurde gezeigt, dass Graphen auf molekular modifiziertem Glimmer lokal auf der Nano-Skala dehnbar ist. Dabei wurde der Glimmer durch das Aufbringen von dendronisierten Polymeren verschiedener Generationen auf Nanometer-Skala modifiziert. Dies eröffnet neue Möglichkeiten, die lokalen elektronischen Eigenschaften von Graphen durch Dehnung zu kontrollieren.Schließlich wurden Kohlenstoff-basierte leitfähige Tinten hergestellt, daraus transparente Elektroden hergestellt, und die Formulierungen der Tinten für das Drucken auf Plastiksubstrate optimiert. / This work focusses on the electronic properties of graphene on the one hand, and on the application of graphenes and other carbon-based hybrid materials for transparent electrodes on the other hand. Accordingly, the first part of the work, which is the larger one, is of fundamental nature and focusses on the electronic interaction between graphene and mica as a substrate. The second, smaller part deals with the design of novel conductive inks based on graphene and other carbon-based hybrid materials for applications in printed electronics, in particular for the production of transparent electrodes. Graphene on mica is a very well defined system, which provides atomically flat graphene extending over several square micrometers. Layer-dependent surface potential variations of single and few layered graphenes on mica were probed with Kelvin Probe Force Microscopy. This allowed to estimate the screening length of graphene on mica. Local variations of the surface electrostatic potential above single layer graphene, originating from confined fluid interfacial monolayers of water between the mica and the graphene, were monitored with Scanning Force Microscopy, Electrostatic Scanning Force Microscopy and Raman spectroscopy. This allowed to quantify the doping of graphene by the confined water layers. Exfoliation of graphene onto adsorbed nanostructures on mica allowed to control the strain of graphene at the nano-scale. Nanostructuring was achieved by first coating mica with submonolayers of dendronized polymers of different generations and subsequently depositing graphene. This approach provides new opportunities for the control of the electronic properties of graphene by strain.Finally, novel conducting carbon-based inks were designed and transparent electrodes were fabricated therefrom. The formulations of the inks were optimized for printing on plastic substrates.

Organic electronic devices are receiving growing interest because of their potential to employ lightweight, low-cost materials in a flexible architecture. Typically, indium tin oxide (ITO) is utilized as the transparent positive electrode in these devices due to its combination of high transmission in the visible spectrum and high electrical conductivity. However, ITO may ultimately hinder the full market integration of organic electronics due to its increasing cost, the limited availability of indium, lack of mechanical flexibility, and sustainability with regards to the environment and material utilization. Therefore, alternatives for ITO in organic electronics are currently being pursued. Transparent electrodes comprised of single wall carbon nanotubes (SWNTs) are an appealing choice as a surrogate because of the extraordinary electrical and mechanical properties these 1-D structures posses. As such, the research presented in this dissertation has been conducted to advance the goal of manufacturing SWNT networks with transparent electrode properties that meet or exceed those of ITO. To this end, SWNT films were characterized with regard to the collective and individual optoelectronic properties of the SWNTs that comprise the network. Specifically, corroborative theoretical and experimental observations were employed to expand the understanding of how the optoelectronic properties of polydisperse and monodisperse SWNT networks are enhanced and sustained through chemical treatment and subsequent processing. In addition, the impact of interfacial electrical contact resistance between SWNT electrodes and metallic fingers often used in photovoltaic system applications was elucidated. In summary, the research presented in this dissertation can be leveraged with present state of the art in SWNT films to facilitate future SWNT electrode development.

L'utilisation de matériaux transparents et conducteurs a subi une croissance exponentielle lors de la dernière décennie, puisque faisant partie intégrante de nombreux dispositifs optoélectroniques tels que les écrans tactiles & les cellules solaires. Parmi ces matériaux, l'oxyde d'indium-étain occupe la quasi-totalité du marché puisqu'il associe une conductivité élevée et une transparence supérieure à 90% sous forme de film mince. Cependant, le développement de technologies flexibles pousse à rechercher des alternatives à son utilisation car son cout élevé et sa faible flexibilité le rendent incompatible. Au milieu des alternatives carbonées (graphène et nanotubes), les nanomatériaux métalliques ou les polymères conducteurs se présentent comme des alternatives intéressantes : bas cout et facilité à mettre en forme pour les polymères conducteurs, hautes performances pour les nanofils métalliques. Cette thèse présente la mise en œuvre de ces matériaux alternatifs par la méthode originale d'électrofilage et l'étude de leurs propriétés optoélectroniques. La maitrise des conditions de mise en forme (champ, débit, paramètres environnementaux) et l'optimisation des solutions utilisées (rhéologie, concentration en polymère, co-solvants) nous a permis d'obtenir 2 types de nanostructures : des nanofibres 100% polymériques à base de PEDOT:PSS et des nanofibres composites PVP:Nanofils d'argent. L'étude des propriétés opto-électroniques des réseaux ainsi obtenus a aussi été étudiée / The use of transparent and conductive materials has been growing exponentially in the last decade as they are part of many optoelectronic devices such as touch screens and solar cells. Among these materials, Indium-Tin Oxide (ITO) is the market reference since it combines a low resistivity and a high transparency up to 90% in the form of thin film. However, the growing in the development of flexible technologies created a real need in alternatives as ITO has poor mechanical properties. Carbon nanotubes and graphene are potential substitutes, but metallic nanowires and conductive polymers have been developed for their high performances and low cost respectively.This thesis presents the implementation of these alternatives by the original method of electrospinning and the study of their optoelectronic properties. The optimization of the experimental setup (field, rate, environmental parameters) and solutions (rheology, polymer concentration, co-solvents) allowed us to obtain 2 different kinds of nanostructures: fully polymeric with PEDOT:PSS and composite with PVP and silver nanowires. The study of the optoelectronic properties of the resulting networks has also been investigated

Organic solar cells (OSCs) is an emerging photovoltaic technology that opens up new application areas where common inorganic techniques are not able to score. Some of those key features are flexibility, light weight, semitransparency, and low cost processing. The current industry-standard for the transparent electrode, indium tin oxide (ITO), cannot provide these properties because it is brittle and expensive. This thesis aims to investigate an alternative type of promising transparent electrode: silver nanowire (AgNW) networks. They exhibit similar or even better optical and electrical performance than ITO down to a sheet resistance of 12 Ohm/sq at 84% transmission (including the glass substrate). Furthermore, AgNWs are more flexible, solution-processable, and more cost-effective than ITO. However, two challenges occur during implementation as bottom electrode in OSCs. First, their inherently high roughness causes devices to shunt. Second, the AgNW network structure exhibits – in contrast to the continuous ITO – µm²-sized voids that have to be bridged electrically by the organic layers. In the first part of this thesis, solution-processed small molecule charge transport layers are investigated. In the case of hole transport layers (HTL), the host BF-DPB and the dopant NDP9 are investigated using tetrahydrofuran as a solvent. It is shown that BF-DPB is already doped by NDP9 in solution via the formation of a hybrid molecule complex. Solution-processed layers exhibit similar conductivities as compared to the reference deposition, which is thermal evaporation in high vacuum. The layers sufficiently smoothen the AgNW electrode such that DCV5T-Me:C60 organic solar cells with an efficiency up to 4.4% are obtained. Moreover, the influence of the square micrometer large network voids is investigated using HTLs of varying conductivity. As a result, a minimum conductivity of 1e−4 S/cm is needed to avoid macroscopic performance losses. Equivalent circuit simulations are performed to confirm these results. As a second planarization method, the AgNWs are buried in an insulating polymer that serves concurrently as flexible and ultrathin substrate. Out of three different polymers tested, the optical adhesive ’NOA63’ gives the best results. The roughness is strongly reduced from 30 nm down to (2 ± 1) nm. Two different OSC types are employed as testing devices with fully-flexible alumina encapsulation against moisture ingress. Maximum power conversion efficiencies of 5.0% and 5.6% are achieved with a fullerene-free cascade layer architecture and a DCV5T-Me:C60 OSC, respectively. To evaluate the applicability of these fully-flexible and encapsulated devices, degradation studies are performed under continuous illumination and a humid climate. Although employing the intrinsically stable DCV5T-Me:C60 stack design, within one day a fast degradation of the fully-flexible solar cells is observed. The degradation is attributed to AgNW electrode failure that results from photo-oxidation and -sulfurization, photo-migration, and electromigration. It is further shown that the cascade organic solar cell lacks intrinsic stability. In summary, efficient, fully-flexible, and encapsulated devices are shown. However, in terms of competitive OSCs, the low stability of AgNW electrodes is a challenge to be taken care of. In current research, this issue needs to be addressed more frequently. / Organische Solarzellen (OSZ) sind ein junges Forschungsgebiet der Photovoltaik, welches neue Anwendungsgebiete erschließt, für die herkömmliche anorganische Solarzellen nicht einsetzbar sind. Einige der Haupteigenschaften sind Flexibilität, niedriges Gewicht, Teiltransparenz und geringe Herstellungskosten. Indiumzinnoxid (ITO), der aktuelle Industriestandard transparenter Elektrodentechnologie, ist nicht in der Lage, diese Eigenschaften zu gewährleisten. Dies liegt vor allem an der Brüchigkeit von ITO und der begrenzten Verfügbarkeit von Indium, welche mit einem hohen Preis einhergeht. Das Ziel dieser Dissertation ist die Integration einer alternativen und vielversprechenden Elektrodentechnologie: Netzwerke aus Silbernanodrähten (AgNWs). Mit einem Schichtwiderstand von 12 Ohm/sq bei einer Transmission von 84% (inklusive Glassubstrat) besitzen sie ähnliche oder sogar bessere optische und elektrische Eigenschaften als ITO. Des Weiteren sind AgNW-Elektroden flexibler und kostengünstiger als ITO und aus flüssiger Phase prozessierbar. Es gibt allerdings zwei Herausforderungen, welche die Integration als Grundelektrode in OSZ erschweren. Zum einen sind AgNW-Netzwerke sehr rauh, sodass organische Bauteile kurzgeschlossen werden. Zum anderen weisen AgNW-Elektroden, im Gegensatz zu einer vollflächigen ITO-Schicht, Lücken zwischen den einzelnen Drähten auf. Diese Lücken müssen von den organischen Schichten der OSZ elektrisch überbrückt werden. Im ersten Teil der Arbeit werden daher flüssigprozessierte Ladungsträgertransportschichten aus kleinen Molekülen untersucht, welche die AgNW-Elektroden glätten und die verhältnismäßig großen Lücken füllen sollen. Im Falle von Lochleitschichten (HTL) wird BF-DPB als Matrix und NDP9 als Dotand in Tetrahydrofuran gelöst und zur Anwendung gebracht. BF-DPB wird dabei schon in Lösung von NDP9 dotiert, wobei sich ein Hybridmolekülkomplex ausbildet. Die Leitfähigkeit der entstehenden Schichten ist ähnlich zu Referenzschichten, die durch thermisches Verdampfen im Hochvakuum hergestellt wurden. Die erhaltenen HTLs glätten die AgNW-Elektroden, sodass DCV5T-Me:C60-Solarzellen mit einer Effizienz von maximal 4.4% hergestellt werden können. Weiterhin wird der Einfluss der quadratmikrometergroßen Löcher auf die makroskopische Effizienz der Solarzelle in Abhängigkeit der HTL Leitfähigkeit untersucht. Um signifikante Effizienzverluste zu verhindern, muss der HTL eine minimale Leitfähigkeit von etwa 1e−4 S/cm aufweisen. Simulationen eines Ersatzschaltkreises bestätigen hierbei die experimentellen Ergebnisse. Im zweiten Teil der Arbeit wird eine Planarisierungsmethode untersucht, in welcher die AgNWs in nichtleitfähigen Polymeren eingebettet werden. Diese Polymere fungieren anschließend als flexibles Substrat. Der optische Kleber ”NOA63” erzielt hierbei die besten Ergebnisse. Die Rauheit der AgNW-Elektroden wird von etwa 30 nm auf 1 bis 3 nm stark reduziert. Anschließend werden diese AgNW-Elektroden in zwei unterschiedlichen OSZ Konfigurationen getestet und mit einer vollflexiblen Schicht aus Aluminiumoxid gegen Wasserdampfpermeation verkapselt. Somit können maximale Effizienzen von 5% mithilfe einer organischen Kaskadenstruktur und 5.6% mit DCV5T-Me:C60 OSZ erreicht werden. Um die Anwendbarkeit dieser vollflexiblen und verkapselten OSZ zu bewerten, werden Alterungsstudien unter konstanter Beleuchtung und feuchtem Klima durchgeführt. Es wird gezeigt, dass die in das Polymer eingebettete AgNW-Elektrode aufgrund von Photooxidation und -schwefelung und Photo- und Elektromigration instabil ist. Dieser Sachverhalt ist für die Anwendung von AgNW-Elektroden in kommerziellen OSZ von großer Bedeutung und wurde in der Forschung bisher nicht ausreichend thematisiert.