Dissertationen zum Thema „Encapsulation for electronic“

Barrier coatings are a category of functional films designed to enhance enduse properties to the underlying substrate. When used for electronic applications (such as flexible displays, digital paper, lighting, OLEDs and solar cells), the barrier characteristics are meant to protect the device from environmental influence, especially the permeation of oxygen and water vapour that can degrade and corrode the active layers of the devices (causing mal-functioning). In this project, silicon oxide barrier layers were deposited onto a non-treated BO-PET via plasma enhanced chemical vapour deposition, using a pilot scale roll-to-roll coater. The aim was to optimise the deposited coatings by understanding the effect of the deposition parameters on the barrier properties (oxygen and water vapour barrier) and the surface properties (i.e. topography, chemistry, structure, thickness, mechanical properties) of the coatings. For encapsulation in electronic devices such as OLEDS and photovoltaics cells, the barrier coatings must remain transparent and flexible, which is one of the challenges of this project. This project has demonstrated that the moisture barrier performance of silicon oxide coated BO-PET is dependent on film structure (i.e. porosity), which are linked to the plasma conditions of the deposited film. Lower WVTR could be reached (10-2×g/m2/day) for film produced at high input power (1.6kW), low webspeed (< 0.5m/min) and low ratio oxygen:monomer (between 2 and 3). In these conditions, the coating was rather stoichiometric and exhibited a relatively low carbon content (30% atomic) and similar contents in O and Si (about 30% each). The film type was found to have an influence on the final barrier level, as coatings on planarised and adhesion treated substrates showed better barrier performances than coatings on standard untreated PET. Despite all the development done, barrier levels did not match the requirements (10-5×g/m2day) for electronic encapsulation but showed some promising improvement. Thinner coatings were found to have better barrier against moisture permeation, although a threshold of 800nm was identified as critical thickness above which the WVTR dramatically increased. As far as changing the plasma composition via the addition of CO2 as a reactive gas, a slight decrease in WVTR (improvement in barrier) was observed at low CO2 flow rates (up to 200SCCM). WVTR doubled, however, when increasing the amount of CO2. This increase was associated with a decrease in hardness and increase of carbon content. Alternative power generation, using squared waves instead of sinusoidal, was not successful and deteriorated the barrier performances (higher WVTR). Finally, the route of topcoats to enhance the barrier by filling the pores showed promising results in the case of Al2O3 ALD topcoats but didn't show significant improvement in the case of acrylate topcoats, partly due to a lack of adhesion of the acrylate on the surface of the SiOₓ coating.

Thesis (S.B. and M.Eng.)--Massachusetts Institute of Technology, Dept. of Electrical Engineering and Computer Science, 2000.<br>Includes bibliographical references (p. 65).<br>Long-term success of an implantable retinal prosthesis depends on the ability to hermetically seal sensitive electronics from a saline environment with an encapsulant material. Furthermore, the retinal implant project's proposed laser-driven prosthesis requires that the encapsulation material be transparent. The device itself has two components that must protrude out of the encapsulation material. The first is an electrode array on a polyimide strip. The second is a platinum return wire. Difficulty in finding encapsulation materials has arisen from saline leakage at the interface of the encapsulant and these two protruding components. This thesis addresses the pursuit of materials and bonding strategies suitable to protect the device in chronic submersion. An electrode array lying on a polyimide layer sits flat against the ganglion cells within the eye. Precise stimulation requires that current does not flow between the individual electrode contacts. The array must be tested under chronic saline submersion to ensure that each electrode remains electrically isolated by the polyimide. The electronics package will be supported in the eye by a modified intraocular platform, similar to a device typically used in human cataract surgery. The lens is created by photolithography, a rapid prototyping technique. This platform must conform to surgical needs and structural integrity required by the device. The primary goal of this thesis is to find a flexible transparent encapsulant material. This material must undergo long term leakage tests to ensure that it will be reliable in protecting the microelectronics mounted on the platform before being considered for use. The secondary goal of the thesis is testing of the polyimide electrode array itself to determine its ability to resist saline leaks.<br>by Michael Evans.<br>S.B.and M.Eng.

Over the past forty years, compelling demands for safer, cleaner and more efficient vehicles have given rise to a drastic increase in the replacement of many traditional mechanical and electrical mechanisms by more advanced electronic systems. Due to their harsh operating environments, automotive electronic systems are subject to failures from thermomechanical stresses and corrosive breakdown, adversely affecting their reliability and lifespan. Furthermore, the development of bus communication protocols for improved control capabilities has prompted wider systems distribution within the restricted space of a vehicle and inadvertently led to higher assembly complexity, increased vehicle weight and manufacturing costs. Despite advancements in the industry, no commercially viable process exists that is capable of providing electronic systems with sufficient robustness for their operating environments while also offering assembly consolidation to enable cost reduction. The primary focus of this thesis is the engineering of a low-cost, single-cycle process for the direct encapsulation of electronic systems within thermoplastic structures, leading to the production of robust, geometrically flexible and ready-to-assemble plastic automotive components with integrated electronics and requisite power distribution.

Thesis (Ph.D)--Mechanical Engineering, Georgia Institute of Technology, 2010.<br>Committee Chair: Samuel Graham; Committee Member: Bernard Kippelen; Committee Member: David McDowell; Committee Member: Sankar Nair; Committee Member: Suresh Sitaraman. Part of the SMARTech Electronic Thesis and Dissertation Collection.

Thesis (M.S.)--Worcester Polytechnic Institute.<br>Keywords: packaging; micro electro mechanical systems; MEMS; electronics; die warpage; die bow; encapsulant; encapsulate; electrochemical migration; corrosion; wirebonds. Includes bibliographical references (p. 94-99).

<p> Organic Light Emitting Diodes (OLEDs) are extremely attractive candidates for flexible display and lighting panels due to their high contrast ratio, light weight and flexible nature. However, the materials in an OLED get oxidized by extremely small quantities of atmospheric moisture and oxygen. To obtain a flexible OLED device, a flexible thin-film barrier encapsulation with low permeability for water is necessary. </p><p> Water permeates through a thin-film barrier by 4 modes: microcracks, contaminant particles, along interfaces, and through the bulk of the material. We have developed a flexible barrier film made by Plasma Enhanced Chemical Vapor Deposition (PECVD) that is devoid of any microcracks. In this work we have systematically reduced the permeation from the other three modes to come up with a barrier film design for an operating lifetime of over 10 years. </p><p> To provide quantitative feedback during barrier material development, techniques for measuring low diffusion coefficient and solubility of water in a barrier material have been developed. The mechanism of water diffusion in the barrier has been identified. From the measurements, we have created a model for predicting the operating lifetime from accelerated tests when the lifetime is limited by bulk diffusion. </p><p> To prevent the particle induced water permeation, we have encapsulated artificial particles and have studied their cross section. A three layer thin-film that can coat a particle at thicknesses smaller than the particle diameter is identified. It is demonstrated to protect a bottom emission OLED device that was contaminated with standard sized glass beads. </p><p> The photoresist and the organic layers below the barrier film causes sideways permeation that can reduce the lifetime set by permeation through the bulk of the barrier. To prevent the sideways permeation, an impermeable inorganic grid made of the same barrier material is designed. The reduction in sideways permeation due to the impermeable inorganic grid is demonstrated in an encapsulated OLED. </p><p> In this work, we have dealt with three permeation mechanisms and shown solution to each of them. These steps give us reliable flexible encapsulation that has a lifetime of greater than 10 years.</p>

L’électronique embarquée, notamment les modules de puissance, permet la gestion de l’énergie électrique et donc le développement de véhicules « décarbonés ». Toutefois, en vue d’être positionnés près du moteur thermique, ces composants électroniques devront résister à des environnements très divers et parfois à de sévères contraintes (humidité, agression chimique (huiles), vibrations…). Or, les matériaux d’encapsulation qui les protègent ne sont pas, aujourd’hui, assez performants pour répondre à ces nouvelles contraintes. Ainsi, le but de ces travaux de thèse est donc de développer de nouveaux polymères d’encapsulation. Pour cela, deux types de copolymères Silicone/Polyuréthane (Si/PU) réticulés ont été synthétisés, sans solvant, et avec des temps de polymérisation courts.Une première série de matériaux Si/PU contenant entre 55 et 76%m de motif silicone, a été synthétisée par polyaddition alcool-isocyanate à partir de précurseurs silicone, synthétisés ou commerciaux, et d’un pluriisocyanate, en présence d’un catalyseur. Une seconde série de copolymères Silicone/Polyhydroxyuréthane (Si/PHU) contenant 26 et 61%m de motif silicone a été obtenue sans isocyanate et sans catalyseur, à partir de poly(diméthylsiloxane) biscyclocarbonate et d’une triamine.Les propriétés mécaniques, thermiques et le caractère hydrophobe de tous ces matériaux ont été évalués. Dans le but d’améliorer les propriétés thermiques et de diminuer le coût de la résine d’encapsulation, des charges inorganiques ont été incorporées à certains polymères Si/PU.Les matériaux les plus intéressants ont été testés comme encapsulant dans des modules de puissance et les premières mesures électriques au cours de cyclages thermiques sont très prometteuses<br>Embedded electronics, particularly power modules, allows management of electric energy and therefore development of “carbon-free” vehicle. However, these electronic components, will shortly be located near heat engine automotive, and they must withstand various environments and sometimes, hard stresses (humidity, chemical aggression (oil), vibrations…). But actual encapsulation materials are not today efficient enough to match with these future imposed stresses. Thus, the aim of this work is to develop new encapsulation polymers. For this, two types of crosslinked Silicone/Polyurethane (Si/PU) copolymers were “solvent-free” synthesized and with short polymerization times.A first series of materials Si/PU containing between 55 and 76%wt silicone units were synthesized by alcool-iscyanate polyaddition from silicone precursor, synthesized or commercial, and a pluri-isocyanate, in the presence of catalyst. A second series of copolymers, Silicone/Polyhydroxyurethane (Si/PHU) containing 26 and 61%wt silicone units, was obtained without isocyanate or catalyst from poly(dimethylsiloxane) biscyclocarbonate and a triamine.Mechanical and thermal properties as well as hydrophobic character of all materials were evaluated. In order to improve thermal properties and decrease the cost of encapsulation resin, inorganic fillers were blended in some of Si/PU polymers.The most interesting materials were tested as encapsulant in power modules, and the first electrical measurements during thermal cyclings were very promising

The thesis deals with the pouring of epoxy materials over LED strips. The research part contains an introduction to photometry and summarizes the types of potting compounds along with their characteristics. The practical part delves into the effect different amount of pigment has on the photometric properties. This is assessed based on verified measurements performed with the help of a goniophotometer on samples with different amounts of pigment, which were created using an integration sphere. Furthermore, a brightness analysis and a long-term outdoor test were performed.

This dissertation describes the effective encapsulation of redox active compounds inside deep-cavity cavitands: Gibb's octaacid40 and Rebek's 41 tetracarboxylate cavitand. Gibb's octaacid is a water-soluble, deep-cavity cavitand that forms well-characterized dimeric molecular capsules around hydrophobic guests. Both 1H NMR spectroscopic and voltammetric experiments clearly reveal that ferrocene plays the role of hydrophobic guest effectively. Ferrocene derivatives (ferrocenylmethyltrimethylammonium (FcNMe3+), ferrocenemethanol (FcOH), and ferrocene carboxylic acid (FcCOOH)) were also found to form inclusion complexes with octaacid cavitand however, in this case 1:1 (host to guest) ratio complexes are formed. This is in strong contrast with the dimeric capsule formed around ferrocene. Under the surveyed experimental conditions encapsulated ferrocene is electrochemically silent. We have also found that the negative charges around this dimeric molecular capsule play a very important role. For instance, hydrophobic cations, such as viologens,60 bind to the outer surface of the capsule. This opened a possibility of mediated electron transfer reactions between molecules bound inside the octaacid capsule and tightly attached to its outer surface in purely synthetic system. The cationic ferrocene derivative, ferrocenylmethyltrimethylammonium (FcNMe3+), was used as a mediator since its electrochemical potential range makes it suitable as a mediator molecule. In fact, our data clearly support that FcNMe3+ mediates electron transfer between encapsulated ferrocene and the electrode surface. Ferrocene, its derivatives (FcNMe3+ and FcOH), and cobaltocenium (Cob+) also form 1:1 inclusion complexes with Rebek's tetracarboxylate cavitand, which surprisingly are all voltammetrically silent. The formation of these inclusion complexes seems to be driven by hydrophobic interactions between the host and the guest. The lack of voltammetric response observed in this work is a very intriguing finding.

Abstract This Thesis proposes and describes the use of optical coherence tomography (OCT) as a non-contact and non-destructive characterization technique for printed electronics. It is based on and includes the first published results of such an application of the OCT technique. Several different types of structures were studied to evaluate the feasibility of the application. The measurement data was used to define the surface topography, physical dimensions of the specimen features, and to evaluate the ability to characterize multi-layered and multi-material structures. Presented OCT measurements were done for: screen-printed conductive and insulating structures, microfluidic channels, microscopy glass and organic field effect transistors (OFET), both coated with polymer, and inkjet-printed colour filters. A novel approach to encapsulation inspection was presented. The results show that OCT could be used for full volumetric and non-destructive characterization of the 1-to-2-µm-thin protective layers used in organic and printed electronics. The measurements presented in the Thesis were done using OCT devices in time and in spectral domains. Despite the focus on studying the application of the technique, as a result of observations and limitations of the existing equipment, a new type of OCT device has been developed. A high data acquisition rate of the spectrometer-based systems (SD-OCT) was combined with a broadband supercontinuum light source, used so far mainly in the time-domain (TD-OCT), to enable the sub-micron-resolution spectral domain optical coherence tomography (SMR SD-OCT). The supercontinuum generation effects with virtually white probing light and enables not only superior resolution, but also, e.g., true-colour OCT imaging. The measurements performed on the inkjet-printed colour filters confirm that despite the absorptive properties of the materials, characterization of the few-microns-thin ink layers is possible using visible range of the electromagnetic spectrum and spectral domain OCT. The study shows the potential and versatility of OCT in the printed electronics characterization. In addition, the Thesis discusses further development of the technique, needed to fully match the challenging requirements of the on-line quality inspection<br>Tiivistelmä Väitöstyössä sovelletaan optista koherenssitomografiaa (OCT) painetun elektroniikan kontaktittomaan ja kohdetta rikkomattomaan karakterisointiin. Väitöstyö pohjautuu tuloksiin, joissa OCT-tekniikkaa on hyödynnetty ensimmäistä kertaa painettavan elektroniikan rakenteen karakterisoinnissa. Tekniikan soveltuvuutta tutkittiin mittaamalla useita erilaisia näytteitä. Mitattua dataa käytettiin pinnan topografian ja näytteen dimensioiden määritykseen. Lisäksi tutkittiin tekniikan soveltuvuutta monikerrosrakenteiden ja useista eri materiaaleista koostuvien näytteiden mittaukseen. OCT-mittaukset tehtiin seuraaville näytteille; silkkipainetuille johteille ja eristeille, mikrokanaville, polymeerillä päällystetyille mikroskooppilaseille ja orgaanisista aineista valmistettu kanavatransistoreille (OFET) sekä mustesuihkutulostimella valmistetuille värisuodattimille. Orgaaniset materiaalit ja painettava elektroniikka suojataan yleensä koteloinnilla. Tässä väitöstyössä esitellään uusi menetelmä koteloinnin tarkastukseen. Tulokset osoittavat, että OCT-tekniikkaa voidaan hyödyntää 1-2 mikrometrin paksuisen eristekerroksen volumetrisen rakenteen karakterisointiin kohdetta rikkomatta. Tässä väitöstyössä tehdyt mittaukset tehtiin aika- ja spektritason OCT-laitteilla. Huolimatta siitä, että väitöskirjatutkimus keskittyi tekniikan uusiin sovelluksiin, väitöstyössä havaittiin käytettävissä olevien laitteiden puutteellisuudet, jonka vuoksi myös uusi OCT-laite kehitettiin. Spektrometriin pohjautuvan OCT-systeemin (SD-OCT) nopeus yhdistettiin laajakaistaisen supercontinuum valonlähteen kanssa, jota on käytetty aikaisemmin käytännössä vain aikatason OCT-laitteissa (TD-OCT). Laajakaistainen valonlähde mahdollistaa jopa alle mikrometrin syvyyssuuntaisen resoluution. Supercontinuum valonlähde tuottaa käytännöllisesti katsoen valkoista valoa, joka mahdollistaa sekä erinomaisen tarkkuuden, että objektin luonnollisen värin mittaamisen. Mittaustulokset värisuodattimilla osoittavat, että vaikka suodattimissa käytetyt materiaalit absorpoivat spektritason OCT:ssa hyödynnettyä näkyvän aallonpituusalueen spektriä, tekniikalla on mahdollista mitata muutamien mikrojen paksuisia värisuodatinkalvoja. Väitöstutkimus osoittaa OCT-tekniikan monipuolisuuden ja mahdollisuudet painettavan elektroniikan karakterisoinnissa. Lisäksi väitöstyö käsittelee tekniikan jatkokehitystä, jotta se voisi vastata mahdollisimman hyvin reaaliaikaisen laadunvalvonnan tarpeisiin

Within healthcare there is a market pull for biomedical devices that can rapidly perform laboratory processes, such as diagnostic testing, in a hand-held format. For this reason, biomedical devices must become smaller, more sophisticated, and easier to use for a reasonable cost. However, despite the accelerating academic research on biomedical microdevices, and especially plastic-based microfluidic chips, there is still a gap between the inventions in academia and their benefit to society. To bridge this gap there is a need for new materials which both exhibit similar properties as industrial thermoplastics, and that enable rapid prototyping in academia. In this thesis, thiol-ene and thiol-ene-epoxy thermosets are evaluated both in terms of their suitability for rapid prototyping of biomedical microdevices and their potential for industrial manufacturing of “lab-on-chips”. The first part of the thesis focuses on material development of thiol-ene and thiol-ene-epoxy thermosets. Chemical and mechanical properties are studied, as well as in vitro biocompatibility with cells. The second part of the thesis focuses on microfabrication methods for both thermosets. This includes reaction injection molding, photostructuring, and surface modification. It is demonstrated how thiol-ene and thiol-ene-epoxy both provide advantageous thermo-mechanical properties and versatile surface modifications via “thiol-click chemistry”. In the end of the thesis, two applications for both polymer platforms are demonstrated. Firstly, thiol-ene is used for constructing nanoliter well arrays for liquid storage and on-demand electrochemical release. Secondly, thiol-ene-epoxy is used to enhance the biocompatibility of neural probes by tuning their flexibility. It is concluded that both thiol-ene and thiol-ene-epoxy thermosets exhibit several properties that are highly suitable for rapid prototyping as well as for scalable manufacturing of biomedical microdevices.<br><p>QC 20171003</p>

L'introduction du transistor à un électron (SET) a secoué l'industrie des semi-conducteurs, avec des promesses d'efficacité inégalée. Cependant, le coût et la complexité associés à la réalisation d'un fonctionnement stable ont fortement entravé leur adoption. Après être tombé en dehors des grâces de l'industrie, la recherche universitaire a continué à pousser, démontrant des techniques novatrices pour la création de SET. Au cœur de ce problème de stabilité, il y a le besoin de construire de manière contrôlable des nanoislands de moins de 10 nm. Parmi les méthodes disponibles pour cette formation nanoisland, le dépôt de couche atomique (ALD) se distingue comme un processus hautement contrôlable industriellement. La deuxième barrière à l'entrée est la création d'électrodes nanogap, utilisées pour injecter du courant à travers ces nanoislands, pour lesquelles les chercheurs se sont largement appuyés sur des techniques de fabrication non évolutives comme la lithographie par faisceau d'électrons et le faisceau ionique focalisé. La technique d'évaporation de bord d'ombre surmonte les problèmes de complexité et d'échelle de la fabrication de nanogap, ouvrant de nouvelles possibilités. Dans ce travail, ALD sera démontré comme une superbe technique pour la culture de vastes réseaux 3D de nanoparticules de platine sous 2nm encapsulées dans Al2O3. ALD a fourni un moyen de faire croître ces matrices de nanoparticules en un seul processus, sous vide et à basse température. Grâce à l'évaporation du bord d'ombre, la lithographie UV a ensuite été utilisée pour former des électrodes nanogap avec des largeurs latérales élevées (100μm), avec des écarts démontrés au-dessous de 7 nm. La combinaison de ces techniques aboutit à un procédé de fabrication à haut rendement et à faible besoin pour la construction de SET complets. A partir des transistors résultants, de fines lamelles ont été préparées à l'aide de FIB et des modèles 3D ont été reconstruits par tomographie TEM pour analyse. La caractérisation électrique a été effectuée jusqu'à 77K, avec une modélisation révélant le transport de Poole-Frenkel en parallèle à un éventuel cotunneling. Des blocus de Coulomb stables, la signature des SET, ont été observés avec une périodicité régulière et étaient identifiables jusqu'à 170K. L'optimisation de ce processus pourrait produire des SETs de surface élevée capables de fonctionner de manière stable à température ambiante<br>The introduction of the single electron transistor (SET) shook the semiconductor industry, with promises of unrivaled efficiency. However, the cost and complexity associated with achieving stable operation have heavily hindered their adoption. Having fallen out of the graces of industry, academic research has continued to push, demonstrating novel techniques for SET creation. At the core of this stability issue is a need to controllably build nanoislands smaller than 10nm. Among the methods available for this nanoisland formation, atomic layer deposition (ALD) sets itself apart as an industrially scalable, highly controllable process. The second barrier to entry is the creation of nanogap electrodes, used to inject current through these nanoislands, for which researchers have leaned heavily on non-scalable fabrication techniques such as electron beam lithography and focused ion beam. The shadow edge evaporation technique overcomes the complexity and scaling issues of nanogap fabrication, opening new possibilities. In this work, ALD will be demonstrated as a superb technique for growing vast 3D arrays of sub 2nm platinum nanoparticles encapsulated in Al2O3. ALD provided a means of growing these nanoparticle matrices in a single process, under vacuum, and at low temperatures. Through shadow edge evaporation, UV lithography was then utilized to form nanogap electrodes with high lateral widths (100µm), with gaps demonstrated below 7nm. The combination of these techniques results in a high yield, low requirement fabrication process for building full SETs. From the resulting transistors, thin lamellas were prepared using FIB and 3D models were reconstructed via TEM tomography for analysis. Electrical characterization was performed down to 77K, with modeling revealing Poole-Frenkel transport alongside possible cotunneling. Stable Coulomb blockades, the signature of SETs, were observed with regular periodicity and were identifiable up to 170K. Optimization of this process could yield high surface area SETs capable of stable operation at room temperature

Les composants hyperfréquences embarqués dans des satellites utilisent actuellement l'encapsulation hermétique dans des boîtiers métalliques ou céramiques. La très forte amélioration des matériaux organiques en termes de dégazage et d'impureté ionique notamment rend possible l'utilisation de solutions quasi-hermétiques pour l'environnement spatial. Les encapsulations plastiques ouvrent des perspectives avérées de gain de dimension et de coût. La validation d'une technologie d'encapsulation repose sur la réalisation d'essais de fiabilité normatifs (1000 heures à 85°C et 85% d'humidité relative). Ces essais sont applicables quels que soient le profil de stockage de la mission, le type d'encapsulation et la technologie des composants utilisés. Les conditions de réalisation de ces essais ne sont pas clairement définies, par exemple l'application ou pas d'un fort champ électrique au niveau du composant. Or ce seul paramètre devient prépondérant lorsque les conditions sont réunies pour permettre la mise en place de phénomènes de corrosion. Ces travaux de thèse se sont axés sur la compréhension des mécanismes de défaillance mis en jeu dans des tests de vieillissement accéléré en chaleur humide. Pour cela, une méthodologie a été mise en œuvre pour établir les signatures électriques en statique de composants défaillants de deux filières technologiques de MMICs GaAs. Ces tests ont été reproduits sur des composants avec et sans encapsulation par une résine époxyde chargée silice, déposée selon le procédé dam-and-fill. Ainsi, il a été possible de distinguer les défaillances liées à la dégradation intrinsèque des composants, de l'effet protecteur ou non de l'encapsulation plastique. En parallèle, le comportement d'échantillons de résines sous différentes ambiances de chaleur humide a été testé et une modélisation a été proposée pour prédire leur prise d'humidité. Concernant l'effet de l'encapsulation par dam-and-fill, les résultats obtenus ont été contradictoires et dépendant des lots de composants. Ces résultats sont à pondérer par la taille restreinte de l'échantillonnage des files de test. En effet, pour la technologie représentative de cette étude, la présence d'une encapsulation plastique, pour un premier lot de composants, a eu tendance d'une part, à ne pas éviter ni même retarder l'apparition de fuites électriques, et d'autre part à aggraver ces dégradations, au point de mener à des défaillances dans la majorité des cas. De plus, des doutes subsistent sur la qualité de ce lot, notamment celle de la passivation. Pour un second lot de composants testés de technologie identique, il a été observé une amélioration de la résistance à l'humidité des composants encapsulés, vis-à-vis des puces nues. L'analyse de défaillance des composants encapsulés est extrêmement difficile car il faut pouvoir accéder aux défauts à la surface, voire sous la surface, du composant protégé. Une solution alternative a donc été cherchée afin de contourner les problèmes posés par la présence du matériau d'encapsulation. La nouvelle approche proposée combine la thermographie infrarouge avec la méthode du point chaud, l'imagerie en optique et l'analyse aux rayons X. Le défaut est tout d'abord localisé par la face avant, malgré la présence de la résine d'encapsulation. Ensuite, la transparence du substrat GaAs aux infrarouges permet des observations par la face arrière du composant. Une méthodologie de préparation relativement simple et rapide a pu être proposée et sa faisabilité démontrée.

Elektronische Bauteile aus organischen Halbleitern stellen höchste Anforderungen an die Qualität der Verkapselung, die sie vor eindringenden Wasser- und Luftmolekülen schützt. Gleichzeitig soll diese preiswert und mechanisch flexibel sein. Diese Arbeit realisiert Aluminium-Mehrschichtsysteme als wirkungsvolle, biegsame und einfache Verkapselung. Es werden verschiedene Herstellungsmethoden und Zwischenschichtmaterialien untersucht, wobei die Barrierelamination als überlegenes Verfahren etabliert wird. Verkapselungssysteme werden mittels optischer Untersuchung und mit dem elektrischen Calciumtest auf ihre Güte geprüft, bevor sie in Solarzellenalterungsexperimenten unter realitätsnahen Bedingungen zur Anwendung kommen. Laminationsbarrieren aus Aluminiumdünnschichten zeigen reproduzierbar Wasserdampfdurchtrittsraten im unteren 10^(-4) g(H2O)/m^2/Tag-Bereich unter beschleunigten Permeationsbedingungen. Sie verlängern die T(50)-Lebensdauer von Solarzellen um einen Faktor 50 gegenüber unverkapselten Zellen auf Werte, die mit starrer Glas- oder zeitaufwendiger ALD-Verkapselung vergleichbar sind<br>Organic electronic devices require excellent encapsulation to protect them from intruding water- and air-molecules. At the same time, the encapsulation has to be inexpensive and flexible. This work presents aluminum multilayer barriers as highly effective, flexible and low-cost encapsulation. Various production methods and interlayer materials are investigated and barrier-lamination is established as superior process. Encapsulation systems are evaluated optically and by means of the electrical calcium-test, before they are employed in realistic solar cell aging experiments. Lamination-barriers of thin aluminum films show reproducible water-vapor transmission rates in the low 10^(-4) g(H2O)/m^2/day-range under accelerated permeation conditions. They improve the T(50)-lifetime of solar cells by a factor of 50 compared to unencapsulated cells, reaching values on par with rigid glass encapsulation or time-consuming atomic layer deposition

Ce travail porte sur l'étude du mélange thermodurcissable - thermoplastique (époxyamine / polyetherimide avec séparation de phase) pour évaluer les performances électriques et thermiques. Ces matériaux seraient des nouveaux candidats pour remplacer la couche d'encapsulation dans les semi-conducteurs, par exemple ceux utilisés comme interrupteur dans les applications électroniques de puissance. Les mélanges de polymères seraient un nouveau candidat en tant qu'isolant pour le système. La matrice epoxy-amine seul et les melanges epoxy / Polyetherimide on été caractérisés par microscopie électronique à transmission, microscopie électronique à balayage, Calorimétrie différentielle à balayage, analyse thermogravimétrique, analyse mécanique dynamique, analyse diélectrique avec simulation analytique et des mesures de conductivité électrique et de tension de claquage ont également été entreprises. Ces techniques complémentaires ont d'abord été utilisées pour étudier la séparation de phases et ensuite pour quantifier la taille des nodules de thermoplastiques dans la matrice thermodurcissable. Cette séparation de phase a été examiné et a montré une diminution des valeurs diélectriques de 15% et une augmentation de la tension de claquage par rapport au système époxy-amine pur<br>This work deals with the study of thermoset-thermoplastic blend (epoxy-amine/poly-etherimide phase separated) to assess the electrical and thermal performances. These materials would be new candidates to replace the encapsulation layer in semiconductors, for example ones used as switches in power electronic applications. Polymers blends would be a novel candidate as an insulator for the system. Pure epoxy system as well as Epoxy/Polyetherimide blends where characterized by transmission electron microscopy, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, dynamic mechanical analysis, dielectric analysis with analytical simulation, electrical conductivity and breakdown voltage measurements. These complementary techniques were used first to investigate the presence of the phase separation phenomenon and secondly to quantify the separated nodules size. The effect of this phase separation was examined and showed a decrease in the dielectric values of 15 % and an increase in the breakdown voltage compared to the pure epoxy system. It was finally simulated to show a close assumption of what is found experimentally

As interessantes propriedades eletrônicas, mecânicas e óticas dos materiais orgânicos conjugados fizeram emergir diversas aplicações tecnológicas e comerciais em dispositivos baseados nesses materiais, tais como sensores, memórias, células solares e diodos emissores de luz poliméricos (LEDs). Neste sentido, o tema central desta tese é o estudo das propriedades elétricas e morfológicas e os mecanismos de transporte eletrônico de cargas no PEDOT:PSS, uma blenda polimérica que consiste de um policátion condutivo, o poli(3,4- etilenodioxitiofeno) (PEDOT) e do poliânion poli(estirenosulfonado) (PSS). PEDOT:PSS é amplamente usado como material de eletrodo em aplicações na área de eletrônica plástica, como mencionado anteriormente. Apesar da condutividade elétrica dos filmes finos de PEDOT:PSS possa variar várias ordens de grandeza, dependendo do método pela qual é processado e transformado em filme fino, as razões para este comportamento é essencialmente desconhecido. Esta tese descreve um estudo detalhado do transporte eletrônico de cargas anisotrópico e sua correlação com a morfologia, as condições e as dimensões da separação de fase entre os dois materiais, PEDOT e PSS. Antes de abordar as propriedades do PEDOT:PSS, uma camada de filme fino inorgânica usada para aumentar o tempo de vida de dispositivos orgânicos é descrita no Capítulo 2. Um importante mecanismo de degradação em LEDs poliméricos é a fotooxidação da camada ativa. Assim, isolar a camada ativa da água, oxigênio e luz, torna-se crucial para o aumento do tempo de vida. Um sistema de deposição química a partir da fase de vapor estimulada por plasma (PECVD) é usado para depositar filmes finos de nitreto de carbono em baixas temperaturas, menores que 100 °C, sobre PLEDs com a intenção de aumentar o tempo de vida destes dipositivos e diminuir a fotodegradação do poli[2-metoxi-5- (2-etil-hexiloxi)-p-fenileno vinileno] (MEH-PPV) em ambiente atmosférico. O filme fino de nitreto de carbono possui as características de um material que pode bloquear a umidade e que tem espessura e flexibilidade adequados para a nova geração de PLEDs flexíveis. As características dos filmes finos de nitreto de carbono e MEH-PPV foram investigadas usando-se técnicas de espectroscopia ótica, com particular ênfase no processo de degradação do MEHPPV sob iluminação. Os resultados mostraram que o filme fino de nitreto de carbono protege o filme polimérico e diminui consideravelmente a fotooxidação. Para avaliar o efeito do encapsulamento em dispositivos reais, LEDs poliméricos foram fabricados e pelas curvas de corrente-tensão um aumento no tempo de vida é confirmado quando a camada de nitreto de carbono é presente. O tempo de vida desejado, maior que 10.000 horas, para aplicações comerciais não foi atingido, entretanto, o encapsulamento pode ser melhorado otimizando as propriedades da camada de nitreto de carbono e combinando-as com camadas de outros materiais orgânicos e inorgânicos. Os capítulos seguintes deste trabalho aborda os estudos realizados com o PEDOT:PSS, uma vez que é amplamente usado em eletrônica orgânica, mas relativamente tem recebido pouca atenção com respeito ao transporte eletrônico de cargas, bem como sua correlação com a morfologia. No Capítulo 3, experimentos com microscopia de varredura por sonda (SPM, Scanning Probe Microscopy) e medidas de condutividade macroscópica são utilizados para estudar e obter um modelo 3D morfológico completo que explica, qualitativamente, a condutividade anisotrópica observada nos filmes finos de PEDOT:PSS depositados pela técnica de spin coating. Imagens topográficas de microscopia de varredura por tunelamento (STM) e imagens da seção transversal observadas com o microscópio de forca atômica (X-AFM) revelaram que o filme fino polimérico é organizado em camadas horizontais de partículas planas ricas em PEDOT, separadas por lamelas quasi-contínuas de PSS. Na direção vertical, lamelas horizontais do isolante PSS reduzem a condutividade e impõe o transporte eletrônico a ser realizado por saltos em sítios vizinhos próximos (nn-H, nearest-neighbor hopping) nas lamellas de PSS. Na direção lateral, o transporte eletrônico via saltos 3D em sítios a longas distâncias (3D-VRH, variable range hopping) ocorre entre as ilhas ricas em PEDOT que são separadas por barreiras muito mais finas de PSS, causando um aumento da condutividade nesta direção. Esta discussão é estendida ao Capítulo 4 com uma descrição quantitativa do transporte eletrônico de cargas predominantes. Particularmente, é demonstrado que o transporte de cargas via saltos 3D em sítios a longas distâncias ocorre entre ilhas ricas em PEDOT e não entre segmentos isolados de PEDOT ou dopantes na direção lateral, enquanto que na direção vertical o transporte de cargas via saltos em sítios vizinhos próximos ocorre dentro das lamelas do quasi-isolante PSS. Em algumas aplicações, faz-se necessário usar PEDOT:PSS com alta condutividade elétrica. Isso pode ser feito adicionando-se sorbitol à solução aquosa de PEDOT:PSS. Após um tratamento térmico, e dependendo da quantidade de sorbitol adicionado, a condutividade aumenta várias ordens de grandeza e as causas e consequências de tal comportamento foram investigadas neste trabalho. O Capítulo 5 investiga as várias propriedades tecnológicas do PEDOT:PSS altamente condutivo tratado com sorbitol, tais como a própria condutividade, os efeitos dos tratamentos térmicos e exposição à umidade. É observado que o aumento da condutividade elétrica, devido à adição de sorbitol na solução aquosa, é acompanhado por uma melhoria na estabilidade da condutividade elétrica em condições atmosféricas. Surpreendentemente, a condutividade elétrica do PEDOT:PSS, sem tratamento com sorbitol (~ 10-3 S/cm), aumenta mais de uma ordem de grandeza sob ambiente úmido de 30-35 % umidade relativa. Este efeito é atribuido a uma contribuição iônica à condutividade total. Análise Temogravimetrica (TGA), espectrometria de massa com sonda de inserção direta (DIP-MS) e análise calorimétrica diferencialmodulada (MDSC) foram usadas como técnicas adicionais para o entendimento dos estudos deste Capítulo. No Capítulo 6, microscopia de varredura por sonda-Kelvin (SKPM) foi empregada para medir o potencial de superfície dos filmes finos de PEDOT:PSS tratados com diferentes concentrações de sorbitol. Mostra-se que a mudança no potencial de superfície é consistente com uma redução de PSS na superfície do filme fino. Para estudar o transporte eletrônico nos filmes finos de PEDOT:PSS altamente condutivos tratados com sorbitol, o Capítulo 7 usa medidas de temperatura e campo elétrico em função da conduvitidade correlacionados com analises morfológicas realizadas por STM. É observado que o transporte eletrônico por saltos, na direção lateral, muda de 3D-VRH para 1D-VRH quando o PEDOT:PSS é tratado com sorbitol. Esta transição é explicada por uma auto-organização das ilhas ricas em PEDOT em agregados 1D, devido ao tratamento com sorbitol, tornando-se alinhadas em domínios micrométricos, como observado pelas imagens de STM.<br>Employing the unique mechanical, electronic, and optical properties of the conjugated organic and polymer materials several technological and commercial applications have been developed, such as sensors, memories, solar cells and light-emitting diodes (LEDs). In this respect, the central theme of this thesis is the electrical conductivity and mechanisms of charge transport in PEDOT:PSS, a polymer blend that consists of a conducting poly(3,4-ethylenedioxythiophene) polycation (PEDOT) and a poly(styrenesulfonate) polyanion (PSS). PEDOT:PSS is omnipresent as electrode material in plastic electronics applications mentioned above. Although the conductivity of PEDOT:PSS can vary by several orders of magnitude, depending on the method by which it is processed into a thin film, the reason for this behavior is essentially unknown. This thesis describes a detailed study of the anisotropic charge transport of PEDOT:PSS and its correlation with the morphology, the shape, and the dimension of the phase separation between the two components, PEDOT and PSS. Before addressing the properties of PEDOT:PSS, a new barrier layer is described in Chapter 2 that enhances the lifetime of organic devices. An important degradation mechanism in polymer LEDs is photo-oxidation of the active layer. Hence, isolating the active layer from water and oxygen is crucial to the lifetime. Plasma-enhanced chemical vapor deposition (PECVD) is used to deposit a thin layer of carbon nitride at low deposition temperatures, below 100 °C, on a polymer LED that uses poly[2-methoxy-5-(2´-ethylhexyloxy)-1,4- phenylene vinylene] (MEH-PPV) as active layer. A thin layer of carbon nitride acts as barrier for humidity, but is still sufficiently bendable to be used in flexible polymer LEDs. The characteristics of carbon nitride and MEH-PPV films have been investigated using optical spectroscopy, with particular emphasis on the degradation process of MEH-PPV under illumination. The measurements show that the carbon nitride coating indeed protects the polymer film and diminishes the photo-oxidation considerably. To study the effect of the encapsulation in real devices, polymer LEDs were made and their current-voltage characteristics confirm the enhanced lifetime in the presence of a carbon nitride barrier layer. However, the target, a lifetime of more than 10,000 hours for commercial applications, was not achieved. The remaining chapters of this thesis describe the investigations of PEDOT:PSS. PEDOT:PSS is widely used in organic electronics. So far, relatively little attention has, been paid to the mechanisms of charge transport in this material and the correlation of those properties to the morphology. In Chapter 3, scanning probe microscopy (SPM) and macroscopic conductivity measurements are used to obtain a full 3D morphological model that explains, qualitatively, the observed anisotropic conductivity of spin coated PEDOT:PSS thin films. Topographic scanning probe microscopy (STM) and cross-sectional atomic force microscopy images (X-AFM) reveal that the thin film is organized in horizontal layers of flattened PEDOT-rich particles that are separated by quasi-continuous PSS lamella. In the vertical direction, the horizontal PSS insulator lamellas lead to a reduced conductivity and impose nearest-neighbor hopping (nn-H) transport. In the lateral direction, 3D variable-range hopping (3D-VRH) transport takes place between PEDOT-rich clusters which are separated by much thinner barriers, leading to an enhanced conductivity in this direction. This discussion is extended in Chapter 4, where a quantitative description of the length scales of the predominant transport is obtained. Particularly, it is demonstrated that the hopping process takes place between PEDOT-rich islands and not between single PEDOT segments or dopants in the lateral direction, whilst in the vertical direction the current limiting hopping transport occurs between dilute states inside the quasi-insulating PSS lamellas. By a post-treatment it is possible to modify PEDOT:PSS to raise its conductivity, by orders of magnitude. Typically, the addition of sorbitol to the aqueous dispersion of PEDOT:PSS that is used to deposit thin films via spin coating leads to an enhancement of the conductivity after thermal annealing. The causes and consequences of such behavior were investigated in detail. Chapter 5 describes the various properties of the highly conductive sorbitol-treated PEDOT:PSS, such as the conductivity itself, and the effects of thermal annealing and exposure to moisture. It is found that the conductivity enhancement upon addition of sorbitol is accompanied by a better environmental stability. Surprisingly, the electrical conductivity of PEDOT:PSS thin films without sorbitol treatment is increased by more than one order of magnitude in an environment with more than 30-35 % relative humidity. This effect is attributed to an ionic contribution to the overall conductivity. Thermal gravimetric analysis (TGA), direct insert probe-mass spectrometry (DIP-MS) and modulation differential scanning calorimetry (MDSC) were used as additional tools to demonstrate that, after thermal treatment, the concentration of sorbitol in the final PEDOT:PSS layer is negligibly small. In Chapter 6, scanning Kelvin probe microscopy (SKPM) is employed to measure the surface potential and work function of this PEDOT:PSS films that were deposited from water with different sorbitol concentrations. It is shown that work function of PEDOT:PSS is reduced with increasing sorbitol concentration. This shift can be explained by and is in agreement with- a reduction in the surface enrichment with PSS of the film. To study the charge transport properties of the highly conductive sorbitoltreated PEDOT:PSS films, temperature dependent and electric field dependent measurements are correlated with morphological analysis by STM in Chapter 7. It is found that by sorbitol treatment the hopping transport changes from 3DVRH to 1D-VRH. This transition is explained by a sorbitol-induced selforganization of the PEDOT-rich grains into 1D aggregates that are aligned within micrometer sized domains, as observed in STM images.

碩士<br>淡江大學<br>資訊與圖書館學系<br>92<br>The study is aimed to sum up the concepts of Victorian Electronic Records Strategy from Australia through research articles and content analysis. The study also evaluates the feasibility of our government’s using encapsulation as the electronic records preservation approach through in-depth interviews. The conclusions are as follows: 1.VERS is totally designed for the long-term preservation of the electronic records. And it is a very thorough scheme, which has been implemented for years and still on-going. 2.Encapsulation strategy is a data-oriented electronic records preservation approach, which solves the fast program obsolescence problem and preserves the context, authenticity, and integrity of the records. 3.The use of security system, such as watermark, public key infrastructure, private key infrastructure, electronic signature, certification authority, guarantees the safety of the records and the system. 4.Private organizations, companies, and schools can also use encapsulation strategy. The study has the following recommendations: 1.Every organization should choose appropriate metadata according to various properties of encapsulated objects. 2.According to the Chinese code comparison, Chinese metadata recommends Unicode. However, in Taiwan we use various codes. Therefore, we should establish a conversion program and unify the use of Unicode in the near future. 3.To tackle the program obsolescence problem, the government should set up electronic records long-term preservation principles for all organizations to follow. 4.The design of the security system should emphasize the system instead of data encapsulation. This prevents the incident that when the system fails, the encrypted file cannot be opened. 5.In practice, the encapsulation strategy not only can be used for government file long-term preservation, but also serves a design foundation for private organizations and companies to implement their knowledge management system.

碩士<br>淡江大學<br>資訊與圖書館學系碩士班<br>98<br>This study is aimed to sum up concept of research articles analysis and system implementation. We will focus on encapsulation strategy and relative tools for electronic records. Based on academic theory and the physical demand, to investigate how encapsulation strategy can be applied in electronic records long term preservation. Then construct a dynamic electronic records encapsulation model may solve the electronic records long term preservation by the time. The conclusions are as followed： 1.The dynamic encapsulation strategy ensures electronic records long term preservation. 2.The dynamic encapsulation strategy ensures electronic records could be integrity、authenticity、accessibility. 3.The dynamic encapsulation strategy lets the record administrator efficiently to manage long term electronic records preservation. The study has the following recommendations： 1.This proposed study strategy should integrate several tools into one system. 2.Establishment electronic records transformation form schedules and related software menu. 3.Strengthens of education and training and the accomplishment the document to the staffs.

Tremendous advances in the synthesis and functionalization of nanoparticles over the past twenty years have resulted in remarkable discoveries in the field of nanotechnology. One such development is found in quantum dots, semiconductor nanoparticles that exhibit unique optical and electronic properties not found in the bulk. Research efforts associated with the combination of quantum dots and polymers center on uniting the mechanical or processing properties of the polymer with the optical properties of the quantum dot. Simply blending polymers with nanoparticles typically leads to nanoparticle aggregation, which negates the inherent advantageous properties of the quantum dots. The development of organic and polymer ligands for nanoparticle surface modification enables the preparation of dispersed nanocomposites that retain, or even enhance, the original nanoparticle properties. Presented here is the synthesis of functionalized nanoparticles that are tailored for the growth of polymers directly from the particle surface. Initial studies focused on the preparation of nanoparticle-polymer hybrid materials where the nanoparticles were evenly dispersed throughout the polymer. A method was developed to cross-link polymers grafted from the nanoparticle in an encapsulating shell, with the goal of minimizing nanoparticle degradation. In addition, polymerization chemistry from quantum dot surfaces was modified and optimized to produce conjugated polymer-quantum dot composites. The coupling of these two electronically active components gave composite materials with very unique optical properties that hold potential as displays, sensors, and light-emitting materials.

Flexible electronics have received a lot of attention in recent days due to the several possible applications that can be envised. The aim of this work was to produce thin film transistors (TFTs) fully conformal and flexible suitable for skin electronics applications. For that, parylene C was used as a flexible substrate and, since parylene has good electrical properties, being a good insulator, it was also used as dielectric and encapsulation layers of the TFTs, combining all parylene C qualities in one device. Parylene is a semicrystalline polymer, so to study how some parameters such as thickness and temperature influence the crystallinity, X-ray diffraction (XRD) analysis was performed. For parylene as TFT dielectric layer it was concluded that the optimum thickness was between 200 and 300 nm, reaching TFT mobilities between 10 and 15 cm2V-1s-1, ON/OFF ratio higher than 106 and low leakage current smaller than 10-10 A. The use of parylene as a encapsulation layer improves the behavior of the TFTs with more stability and less variability between similar devices. The use of parylene as a substrate does not affect greatly the performance of the devices being a promising material for electronic skin due to its conformal properties. Finally, the peel off of the films was studied and it was concluded that the better option consists in depositing a polyvinyl alcohol (PVA) film at the glass carrier before the parylene substrate deposition.

博士<br>臺灣大學<br>材料科學與工程學研究所<br>98<br>This study utilized atomic layer deposition (ALD) to develop solutions to critical problems of organic electronics, including patterning-enabling and electron-injection- enhancing dual-functioning films for organic light-emitting diodes (OLEDs), gas-permeation barriers for the thin-film encapsulation of organic solar cells (OSCs), and permeation-blocking and electron-collecting dual-functioning films for flexible air-stable OSCs. On OLEDs, we demonstrated that with a 10-Å ALD Al2O3 film overcoated on a poly[1-methoxy-4-(2’-ethyl-hexyloxy)-2,5-phenylenevinylene] (MEH-PPV) electro- luminescent layer, the OLEDs not only withstood an aggressive photolithographic patterning process without any degradation but unprecedentedly showed increased luminous efficiency. Although the ALD precursor, trimethylaluminum (TMA), was found to damage MEH-PPV through addition to MEH-PPV’s vinylene groups, its damaging effect was eliminated by pre-treating the MEH-PPV surface with isopropyl alcohol (IPA), whose hydroxyl groups scavenged TMA throughout the ALD process. On the encapsulation of OSCs, we developed ALD processes that both prevented degradations caused by ambient gases and served as an annealing step that increased the initial power conversion efficiency (PCE) of the cells. With the ALD temperature set at 140 ºC and the deposition time set at 1 hr, OSCs based on blended poly-3- hexylthiophene (P3HT) and [6,6]-phenyl C61 butyric acid-methylester (PCBM), were optimally annealed during encapsulation, achieving a PCE of 3.66%. Encapsulating the cells with a 26-nm Al2O3/HfO2 nanolaminated film overcoated with an epoxy-resin protection layer enabled the cell to obtain an in-air degradation rate that was similar to cell stored in O2/H2O-free atmosphere. The Al2O3/HfO2 nanolaminated structure resolved the problem of hydrolysis-induced aging that occurred in single Al2O3 films, owing to the hydrophobicity of the HfO2 layers. Additionally, extended exposure of the ALD precursors during the ALD process ensured complete coverage of ALD films over the P3HT:PCBM layer at the perimeter of the cells. On flexible air-stable OSCs, we developed low-temperature (90 ºC) ALD ZnO films as both gas barriers and electron-collection layers for P3HT:PCBM-based inverted OSCs. By utilizing a long purge time (25-s) and a low deposition temperature (90 ºC) in the ALD process, we obtained high electron mobility (9.6 cm2/V s) and low carrier concentration (2.1×1017 cm-3) in the ZnO films, thereby optimizing their electron- collecting function and achieving 4.06% PCE in the resultant inverted OSCs. Moreover, when deposited on poly(ethylene terephthalate) (PET) substrates, the ALD ZnO films at 70 nm of thickness showed excellent barrier properties: water vapor transmission rate (WVTR) < 10-3 g/m2 day and helium transmission rate (HeTR) of 5.03 cc/m2 day. This moisture-blocking capability was crucial for achieving air-stable inverted OSCs, as we determined that air-induced degradations of inverted OSCs mainly originated from moisture uptake by the poly(3,4-ethylene-dioxythiophene):polystyrene sulfonate (PEDOT:PSS) layer. Using an 70 nm ALD ZnO film for the electron-collection/barrier dual functions as well as a 26-nm Al2O3/HfO2 nanolaminate as the encapsulation layer, we demonstrated flexible OSCs on PET substrates with initial PCE of 2.77% and with negligible air-induced degradation: the OSCs showed near identical degradation rate as the control devices stored in an O2/H2O-free environment, and they retained 73% of their initial PCE over 1800 hr of storage under a 65 ºC/60% RH accelerated aging condition. The results of my study will facilitate the practical applications of OLEDs and OSCs, as well as other types of organic electronics that require precise patterning, interface engineering and hermetic sealing.

The ultra high barrier films for packaging find applications in a wide variety of areas where moisture and oxygen barrier is required for improved shelf-life of food/beverage products and for microbial free pharmaceutical containers. These materials also find applications in micro electro mechanical systems such as ICs, and for packaging in industrial and space electronics. Flexible and portable organic electronics like OLEDs (Organic Light Emitting Diodes), OPVDs (Organic Photo Voltaic Devices) and dye sensitized solar cells (DSSCs) have a good potential in next generation solar powered devices. In fact, organic insulators, semiconductors, and metals may be a large part of the future of electronics. However, these classes of materials are just an emerging class of materials mainly because of their life time constraints. Thus significant research is required to bring them into the forefront of electronic applications. If the degradation problems can be diminished, then these polymers could play a major role in the worldwide electronic industry. A flexible polymer film itself cannot be used as an encapsulation material owing to its high permeability. While a glass or metal substrate possesses ultra high barrier properties, it cannot be used in many electronic applications due to its brittleness and inflexibility. Polymer/ nanocomposites based hybrid materials are thus a promising class of material that can be used for device encapsulation. Chapter I summarizes some of the recent developments in the polymer/nanocomposites based materials for packaging and specifically its use in flexible as well as portable organic electronic device encapsulation. While the development of low permeable encapsulant materials is a chemistry problem, an engineering/instrumentation problem is the development of an accurate technique that can measure the low levels of permeability required for electronic application. Therefore, there is a keen interest in the development of an instrument to measure permeability at these limits. The existing techniques to measure the low permeabilities of barrier films, their importance and accuracy of measurements obtained by these instruments have been briefly discussed in this chapter. Different polymer based hybrid composite materials have been developed for the encapsulation of organic devices and their materials properties have been evaluated. Broadly, two diverse strategies have been used for the fabrication of the composites: in-situ curing and solution casting. Chapters II, III and IV discuss the fabrication of nanocomposite films based on in-situ curing while chapter V discusses fabrication based on solution casting. In chapter II, amine functionalized alumina was used as a cross-linking agent and reinforcing material for the polymer matrix in order to fabricate the composites to be used for encapsulation of devices. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to elucidate the surface chemistry. Thermogravimetric and CHN analysis were used to quantify the grafting density of amine groups over the surface of the nanoparticles. Mechanical characterizations of the composites with various loadings were carried out with dynamic mechanical analyzer (DMA). It was observed that the composites have good thermal stability and mechanical flexibility, which are important for an encapsulant. The morphology of the composites was evaluated using scanning electron microscopy (SEM) and atomic force microscopy (AFM). The work presented in chapter III is a technique based on grafting between surface decorated γ-alumina nanoparticles and the polymer to make these nanocomposites. Alumina was functionalized with allyltrimethoxysilane and used to conjugate polymer molecules (hydride terminated polydimethylsiloxane) through platinum catalyzed hydrosilylation reaction. As in the previous chapter, the surface chemistry of the nanoparticles after surface modification was characterized by different techniques (FTIR, XPS and Raman). The grafting density of alkene groups over the surface of the modified nanoparticles was calculated using CHN analyzer. Thermal stability of the composites was also evaluated using thermogravimetric analysis. Nanoindentation technique was used to analyze the mechanical characteristics of the composites. The densities of the composites were evaluated using density gradient column and the morphology of composites was evaluated using SEM. All these studies reveal that the composites have good thermal stability and mechanical flexibility and thus can be potentially used for encapsulation of organic photovoltaic devices. In addition, rheological studies of the composites were carried out to investigate the curing reaction. The platinum-catalyzed hydrosilylation reaction was studied using both DSC and rheological measurements. The competitive reactions occurring in the system was also monitored in real time through DSC and rheology. Based on the curing curves obtained from these two studies, the mechanistic detail of the curing process was proposed. In addition, swelling studies and contact angle measurements of the composites were also carried out to determine the capability of these materials as encapsulants. Chapter IV deals with a thermally stable and flexible composite that has been synthesized by following a hydrosilylation coupling between silicone polymer containing internal hydrides and mesoporous silica. The results of the characterization of the composites indicates that the composites are thermally stable, hydrophobic, flexible and can be potentially used for encapsulating flexible electronic devices. Chapter V discusses the solution casting method for the development of composites. This chapter is divided into two parts: Part I discusses the synthesis and characterization of flexible and thermally stable composites using polyvinyl alcohol as the base polymer matrix and reactive zinc oxide nanoparticles as the dispersed phase. Various studies like thermal analysis, mechanical analysis, surface analysis and permeability studies were used to characterize the composite films for their possible use as a passivation material. The material was used to encapsulate Schottky structured devices and the performance of these encapsulated devices under accelerated weathering was studied. Part II of this chapter discusses the fabrication of hybrid organic/inorganic based polymer-composite films, based on polyvinylbutyral (PVB) and organically modified mesoporous silica. PVB and amine functionalized mesoporous silica were used to synthesize the composite. An additional polyol (‘tripentaerythritol’) component was also used to enhance the –OH group content in the composite matrix. The thermal, barrier and mechanical properties of these composites were investigated. The investigation of these films suggests that these can be used as a moisture barrier layer for encapsulation. Chapter VI gives the concluding remarks of the results presented. The advantages as well as disadvantages of the in-situ cured and solution casted films and the scope for future work is discussed in this chapter.

碩士<br>國立臺北科技大學<br>材料科學與工程研究所<br>101<br>Recently, the optoelectronic industry develops rapidly to increase the requirement of thinner and lighter properties for flat panel display products. Undoubtedly, the fabrication of organic light emitting diode (OLED) on flexible plastic substrate was the major technique in the next flat display generation. The encapsulation of organic semiconductor devices with the concept of multilayer films onto the devices and conductors is the major trend of producing thin and light weight devices for the industrial and research. However, ,the low process temperature of the multilayer films onto the devices exhibits with poor film quality and will cause leakage path by moisture and oxygen which will induce the failure of products after the opening process of contact pads. In this study, to minimize the possible leakage path by moisture and oxygen in the devices, a new technique fortifying the lifetime and reliability of flexible device will be introduced on protecting the sidewall of contact pads after the opening process. The study started with the photolithography process producing 100 x100 μm2 pattern devices to simulate the opening position of contact pads. We encapsulated the device by gas barriers that were produced with magnetron-sputtering system. The gas barriers of thin film layer structure are made with SiO2, Al, SiO2/Al, SiO2/Al (two pairs) respectively and etched in blanket way to form the SiO2 spacer films onto the sidewall of contact pads. By measuring the water vapor transmission rate (WVTR, at 32°C and RH 100%), it was found that the gas barriers of the two sidewall of Al/SiO2 (two pairs) performed well to prevent degradation; It was reduced from the original 2.50x10-5 g/m2-day to 1.21x10-5 g/m2-day after processing. This study has successfully developed a simple sidewall structural design barrier technology.

Semiconducting two-dimensional (2D) materials have gained considerable attention in recent years owing to their potential in future electronics. On the one hand, the conventional 2D semiconductors, such as transition metal dichalcogenides (TMDCs (MoS2, WS2, etc.) are being exhaustively studied, on the other hand, search for novel 2D materials is at a rapid pace. In this thesis, we explore 2D materials beyond graphene and TMDCs in terms of their intrinsic electronic properties and underlying charge transport mechanisms. We introduce 2D semiconducting materials of indium selenide (InSe) and gallium selenide (GaSe), and a novel π-d conjugated Fe3(THT)2(NH4)3 metal-organic framework (MOF) as potential candidates for their use as active elements in (opto)electronic applications. Owing to the air-sensitivity of InSe and GaSe, their integration into active devices has been severely constrained. Here, we report a hexagonal boron nitride (hBN) based encapsulation, where 2D layers of InSe and GaSe are sandwiched between two layers of hBN; top hBN passivating the 2D layer from the environment and bottom hBN acting as a spacer and suppressing charge transfer to the 2D layer from the SiO2 substrate. To fabricate the devices from fully encapsulated InSe and GaSe layers, we employ the technique of lithography-free via-contacts, which are metal contacts embedded within hBN flakes. Based on our results, we find that full hBN encapsulation preserves InSe in its pristine form and suppresses its degradation with time. Consequently, the electronic properties of encapsulated InSe devices are significantly improved, leading to a mobility of 30–120 cm2 V−1 s−1 as compared to a mere ∼1 cm2 V−1 s−1 obtained for unencapsulated devices. In addition, encapsulated InSe devices are stable for a prolonged period of time, overcoming their limitation to be air-sensitive. On employing full hBN encapsulation to GaSe, a high photoresponsivity of 84.2 A W−1 at 405 nm is obtained. The full hBN encapsulation technique passivates the air-sensitive layers from various degrading factors and preserves their unaltered properties. In the future, this technique can be applied to other 2D materials that have been restricted so far in their fundamental study and applications due to their environmental sensitivity. MOFs are another emerging class of semiconducting 2D materials investigated in this thesis. They are hybrid materials that consist of metal ions connected with organic ligands via coordination bonds. In recent years, advances in synthetic approaches have led to the development of electrically conductive MOFs as a new generation of electronic materials. However, to date, poor mobilities and hopping-type charge transport dominant in these materials have prevented them from being considered for electronic applications. In this work, we investigate a newly developed π-d conjugated Fe3(THT)2(NH4)3 (THT: 2,3,6,7,10,11-hexathioltriphenylene) MOF. The MOF films are characterized with a direct bandgap lying in the infrared (IR) region. By employing Hall-effect measurements, we demonstrate band-like transport and a record-high mobility of 230 cm2 V−1 s−1 in Fe3(THT)2(NH4)3 MOF films. The temperature-dependent conductivity confirms a thermally activated charge carrier population in the samples induced by the small bandgap of the analyzed MOFs. Following these results, we demonstrate the feasibility of using this high-mobility semiconducting MOF as an active material in thin-film optoelectronic devices. The MOF photodetectors fabricated in this work are capable of detecting wavelengths from UV to NIR (400–1575 nm). The narrow IR bandgap of the active layer constrains the performance of the photodetector at room temperature by band-to-band thermal excitation of the charge carriers. At 77 K, the device performance is significantly improved; two orders of magnitude higher voltage responsivity, lower noise equivalent power, and higher specific detectivity of 7 × 10^8 cm Hz1/2 W−1 are achieved at 785 nm excitation, which is a direct consequence of suppressing the thermal generation of charge carriers across the bandgap. These figures of merit are retained over the analyzed spectral region (400–1575 nm) and are comparable to those obtained with the first demonstrations of graphene and black phosphorus based photodetectors, thus, revealing a promising application of MOFs in optoelectronics.<br>Zweidimensionale (2D) Halbleiter haben dank ihres Potenzials für elektronische Anwendungen in den letzten Jahren große Aufmerksamkeit erregt. Dabei werden einerseits konventionelle 2D-Materialien, wie die Übergangsmetall-Chalkogenide (TMDCs) (MoS2, WS2, usw.) intensiv erforscht. Andererseits schreitet auch die Suche nach neuen 2D-Materialien rasch voran. Diese Dissertation stellt Forschungsergebnisse zu elektrischen Eigenschaften und den zugrundeliegenden Ladungstransportmechanismen von 2D-Materialien jenseits von Graphen und TMDCs vor. Untersucht wurden die 2D-Halbleiter Indiumselenid (InSe) und Galliumselenid (GaSe), sowie eine neuartige π-d konjugierte Metallorganische Gerüstverbindung (Metal-Organic Framework, MOF) Fe3(THT)2(NH4)3. Diese Materialien sind vielversprechende Kandidaten für elektronische und optoelektronische Anwendungen. InSe und GaSe sind besonders luftempfindliche Materialien. Aus diesem Grund ist ihre Verwendung für aktive Bauteile trotz ihrer hervorragenden elektrischen Eigenschaften bis heute sehr begrenzt. In dieser Arbeit wird ein effektives Verkapselungsverfahren vorstellt, bei dem InSe- oder GaSe-2D-Schichten zwischen zwei Schichten aus hexagonalem Bornitrid (hBN) eingebettet werden. Die untere Schicht hBN isoliert das Material vom Substrat Siliziumdioxid (SiO2), während die obere Schicht das 2D-Material luftdicht isoliert. Um Bauteile aus komplett eingekapseltem InSe oder GaSe herzustellen, wurden lithographiefreie, sogenannte via-Kontakte hergestellt. Dies sind Metallkontakte, die bereits vor der Verkapselung in die hBN-Schichten integriert werden. Die hBN-Verkapselung erhält InSe in seiner ursprünglichen Form. Die hier vorgestellten Ergebnisse zeigen, dass sich die elektronischen Eigenschaften von InSe durch Verkapselung signifikant verbessern, was zu elektrischen Mobilitäten von 30–120 cm2 V−1 s−1 gegenüber nur rund ∼1 cm2 V−1 s−1 in unverkapselten Bauteilen führt. Darüber hinaus bleiben die Eigenschaften der verkapselten InSe-Bauteile über einen langen Zeitraum erhalten und degradieren nicht mehr bei Kontakt mit Luft. Die Verkapselung von GaSe ermöglicht den Einsatz in Fotodetektoren, bei einer Wellenlänge von 405 nm wird eine Fotoempfindlichkeit von 84.2 A W−1 gemessen; auch hier bewahrt die Verkapselung die empfindlichen Schichten vor schädlichen Einflüssen und konserviert so ihre unveränderten Eigenschaften. In der Zukunft kann diese Technik auch für andere 2D-Materialien eingesetzt werden, insbesondere für solche, deren Erforschung und Anwendung durch die große Empfindlichkeit bis heute eingeschränkt ist. Darüber hinaus untersucht diese Dissertation mit Metallorganischen Gerüstverbindungen (MOFs) eine zweite Klasse halbleitender 2D-Materialien. MOFs sind hybride Materialien aus Metallionen, die mit organischen Molekülen als Verbindungselementen eine meist kristalline Struktur bilden. In den letzten Jahren haben Fortschritte in der synthetischen Herstellung zur Entwicklung von elektronisch leitfähigen MOFs geführt. Die niedrige Mobilität und der sogenannte hopping-Ladungstransport der gängigsten MOFs haben jedoch verhindert, dass diese für Anwendungen betrachtet wurden. In dieser Arbeit wird eine kürzlich neu entwickelte, π-d-konjugierte Fe3(THT)2(NH4)3 (THT: 2,3,6,7,10,11-hexathioltriphenylene) MOF vorgestellt. Der MOF Film hat eine direkte Bandlücke im Infrarot(IR)-Bereich liegend. Mithilfe von Hall-Effekt-Messungen wurde gezeigt, dass der Transport in den Fe3(THT)2(NH4)3 MOF Filmen mit dem Drude-Modell konsistent ist. Darüber hinaus wird eine bis jetzt nicht übertroffene Mobilität von 230 cm2 V−1 s−1 gemessen. Die Temperaturabhängigkeit der Leitfähigkeit bestätigt, dass die kleine Bandlücke zu thermisch aktivierten Ladungstragerdichten in den Proben führt. Auf Grundlage dieser Ergebnisse wird die Machbarkeit von hochmobilen halbleitenden Fe3(THT)2(NH4)3 MOFs als aktives Material in dünnen optoelektronischen Bauteilen gezeigt. Die hier vorgestellten MOF Fotodetektoren reagieren auf Wellenlängen im UV bis Nahinfrarotspektrum (400–1575 nm). Die schmale Bandlücke schränkt die Leistung des Fotodetektors bei Raumtemperatur durch thermische Band-zu-Band-Anregung der Ladungsträger ein. Bei einer Temperatur von 77 K verbessert sich die Leistung des Detektors signifikant: Bei 785 nm wird eine um zwei Größenordnungen erhöhte Spannungsempfindlichkeit, eine niedrigere äquivalente Rauschleistung sowie eine höhere spezifische Empfindlichkeit von 7 × 10^8 cm Hz1/2 W−1 erhalten. Dies ist eine direkte Konsequenz der Unterdrückung thermischer Anregung von Ladungsträgern über die Bandlücke. Diese Leistungszahlen sind über das analysierte Spektrum (400–1575 nm) gültig und vergleichbar mit den ersten Fotodetektoren auf Grundlage von Graphen und Schwarzem Phosphor. Die Ergebnisse zeigen deutlich das Potenzial von MOFs für optoelektronische Anwendungen.