Die steigende Nachfrage nach erneuerbarer elektrischer Energie erfordert neue photovoltaische Technologien. Effiziente organische Solarzellen mit gemischten, absorbierenden organischen Molekülen wandeln Sonnenlicht in Elektrizität um und die jüngsten Rekorde des Wirkungsgrads zeigen das Potenzial für eine alternative Energieerzeugung. Trotz dieser Durchbrüche führt die Verwendung komplexer organischer Moleküle, die zu einer selbstorganisierten Absorberschicht zusammengemischt werden, zu komplizierten Morphologien, die bisher nur unzureichend abgebildet werden konnten. Die Morphologie hat jedoch einen entscheidenden Einfluss auf die Umwandlung von Photonen in Elektronen und auf den Photostrom, was sich auf die Gesamtleistung der Solarzelle auswirkt. Diese Dissertation ist eine Studie über die Morphologie organischer Dünnfilm-Mischschichten in verschiedenen organischen Solarzellen unter Verwendung analytischer Elektronenmikroskopietechniken (REM, TEM, EDX). In einem weiteren Schritt werden auch die Einflüsse der Mikrostruktureigenschaften dieser im Vakuum abgeschiedenen organischen Solarzellen auf ihre elektronischen Eigenschaften untersucht. Diese Studie umfasst bekannte Zinkphthalocyanin- (ZnPc) und Fulleren (C60) Mischschichten (ZnPc:C60) sowie neu entwickelte Materialien, DTDCTB und NGX gemischt mit C60. Auf mikroskopischer Skala wurde der Einfluss der Abscheidung der oben genannten Schichten auf unterschiedlich erhitzte Substrate, sowie deren Auswirkungen auf die elektronische Leistungsfähigkeit untersucht. Es wurden drei sehr unterschiedliche Wachstumssysteme beobachtet: • Filme mit guter Phasentrennung (ZnPc:C60) • Gut gemischte dünne Schichten (DTDCTB:C60) • Selbstorganisierende Nanodrähte (NGX:C60) Um die gewachsene Mikrostruktur zu erklären werden thermodynamische Modelle zur Erklärung der experimentellen Ergebnisse eingesetzt. Diese Arbeit bietet daher einen Rahmen, der die Planung zukünftiger Experimente leiten kann. Für die in dieser Arbeit untersuchten Schichtsysteme konnte die Korrelation zwischen den Präparationsbedingungen und der Leistungsfähigkeit der Solarzellen durch die beobachtete Mikrostruktur und die Phasenseparation von Donor und Akzeptor gut erklärt werden.:1 MOTIVATION AND INTRODUCTION 5 2 THEORETICAL FUNDAMENTALS 2.1 BASICS OF ORGANIC SOLAR CELLS 2.1.1 Organic semiconductors materials 2.1.2 Working principle of organic solar cells 2.1.3 Characteristic curves of solar cells 2.1.4 Concept of bulk heterojunction 2.1.5 Morphology and phase separation 2.2 RELEVANT LENGTH SCALES IN THE STUDY OF ORGANIC SOLAR CELLS 2.3 THE SCANNING ELECTRON MICROSCOPE 2.3.1 Introduction and working principle 2.3.2 Interaction of primary electrons with sample 2.3.3 Detecting SE and BSE electrons 2.3.4 SEM tool with FIB 2.4 THE TRANSMISSION ELECTRON MICROSCOPE 2.4.1 Working principle and components of TEM 2.4.2 Scattering in TEM 2.4.3 Operation modes in TEM 2.5 ANALYTICAL ELECTRON MICROSCOPY 2.5.1 EDX in TEM 2.5.2 EDX with high-tech detectors 2.6 CHALLENGES OF ELECTRON MICROSCOPY ON ORGANIC MATERIALS 2.6.1 Contrast formation and electron scattering 2.6.2 Damage induced by electron beam 2.6.3 Contrast formation and electron scattering 2.6.4 Necessity of low energy microscopy 3 MATERIALS AND METHODS 3.1 DONORS AND ACCEPTOR 3.1.1 The donor ZnPc 3.1.2 The donor DTDCTB 3.1.3 The donor NGX 3.1.1 The acceptor C60 3.2 FABRICATION OF ORGANIC SOLAR CELL DEVICES AND THIN FILMS 3.2.1 Vacuum deposition 3.2.2 Solar cell devices 3.2.3 Electrical Characterization 3.2.4 Organic thin films on the substrate 3.3 ELECTRON MICROSCOPES AND SAMPLE PREPARATION 3.3.1 Cross-sections using focused ion beam 3.3.2 Experimental details used in TEM/SEM 4 RESULTS AND DISCUSSIONS 4.1 ZNPC AS DONOR MATERIAL 4.1.1 Morphology of ZnPc:C60 thin films 4.1.2 Solar cell devices with ZnPc:C60 active layer 4.1.3 Conclusions and discussion 4.2 DTDCTB AS DONOR MATERIAL 4.2.1 Peculiar performance of the solar cell 4.2.2 Morphology of DTDCTB:C60 thin films 4.2.3 Solar cell devices with DTDCTB:C60 active layer 4.2.4 Conclusions and discussion 4.3 NGX AS DONOR MATERIAL 4.3.1 Morphology of NGX:C60 thin films 4.3.2 Conclusions and discussion 5 CONCLUSION AND OUTLOOK 6 APPENDIX A1 NEAREST NEIGHBOR DISTANCE A2 FROM DARK FIELD TEM IMAGES TO THE ELEMENTAL MAP A3 COMPARING THE COMPOSITION OF DARK AND BRIGHT POINTS IN THE EDX-ELEMENTAL A4 ROUGHNESS MEASUREMENTS FROM EDX IMAGES A5 SPECTROSCOPY MEASUREMENTS ON DTDCTB:C60 7 LISTS 7.1 ABBREVIATIONS 1.: Acronyms B2.: Materials B3.: Symbols 7.2 LIST OF FIGURES 7.3 LIST OF TABLES BIBLIOGRAPHY

L'incertitude entourant la production du pétrole et la pollution associée aux fossiles combustibles ainsi que la série d'accidents bien connus de Three Mile Island, Tchernobyl et Fukushima, en plus que le désir de diversifier les sources d'énergie sont des facteurs importants qui favorisent le développement de la technologie des cellules photovoltaïques. Certaines applications de photovoltaïques organiques sont particulièrement intéressantes à cause de la possibilité d'impréssion des circuits et la création de cellules photovoltaïques flexibles sous la forme d'un ruban adhésif. À la suite des études fondamentales de Tang, que l'on appelle hétérojonction en volume (BHJ), des cellules photovoltaïques ont été créées par une séparation de phase du polymère. Certains appareils BHJ sont déjà disponibles dans le commerce, mais leur efficacité photovoltaïque est encore faible. Afin d'améliorer cette efficacité, nous proposons de modéliser le processus critique par lequel une excitation locale ( « un exciton ») se dissocie pour former une paire électron / trou conducteur. Contrairement à la majorité des physiciens specialiste dans l'état solide impliqués dans l'étude de ce problème qui semble ignorer le caractère non-Born-Oppenheimer typique de cet événement, nous prévoyons de traiter cet événement directement par la modélisation photochimique utilisant la dynamique semiclassique (saut de suface de Tully) avec laquelle nous avons déjà une certaine expérience. Comme l'objectif est la compréhension des systèmes très complexes, nous proposons des calculs exploratoires basées sur la méthode TD-DFTB, une version semiempirique de la théorie de la fonctionnelle de densité en fonction du temps (TD-DFT) pour lequel un de nous est bien connu pour son travail pionnier. L'étude sera menée en collaboration avec le groupe ORGAVOLT des développeurs de méthodes ab initio pour la modélisation des BHJs, et avec des groupes à Singapour intéressés par les BHJs, ainsi qu'avec des groupes en Allemagne spécialisés dans la DFTB. / The uncertainty surrounding petroleum production and the pollution associated with fossil fuels plus the series of well-known accidents of Three Mile Island, Chernobyl and Fukushima plus the desire to diversify energy sources are important factors favoring the development of solar cell technology. For certain applications organic photovoltaics are particularly interesting because (for example) of the possibility of printing these circuits and the creation of flexible solar cells in the form of adhesive tape. Following the seminal studies of Tang, so-called bulk heterojunction (BHJ) solarcells have been created by polymer phase separation. Some BHJ divices are already available commercially but their photovoltaic efficiency is still low. In order to aid in the improving this efficiency, we propose to model the critical process by which a local excitation (an "exciton") dissociates to form a conducting electron/hole pair. In contrast with the majority of solid-state physicists involved in studying this problem who seem to ignore the typically non-Born-Oppenheimer character of this event, we planto treat this event directly by photochemical modeling using semiclassical (Tully-type) surface-hopping dynamics with which we already have some experience. As the objective is the comprehension of highly complex systems, we propose exploratory calculations based on the TD-DFTB method, a semiemprical version of the time-dependent density-functional theory (TD-DFT) for which one of us is well-known for his pioneering work. The study will be carried out in collaboration with the ORGAVOLT group of developers of ab initio methods for modeling BHJs, and with groups in Singapore interested by BHJs, as well as with groups in Germany specializing in DFTB.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21124号 / 工博第4488号 / 新制||工||1697(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 辻井 敬亘, 教授 山子 茂, 教授 竹中 幹人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

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Uppsatsen tar sikte på att undersöka hur dagens aktörer arbetar med grön fastighetsförädling och vilka olika incitament som finns för aktörer att arbeta med detta. Vidare analyserar vi konkret vilka incitament som finns för ägaren av bostadsrättsfastigheter respektive hyresrättsfastigheter att investera i solceller. Vad finns det för likheter och skillnader mellan dessa två upplåtelseformer? Uppsatsen konkretiserar undersökningen genom en fallstudie i samarbete med HSB MälarDalarna. Där genomförs investeringar genom montering av solceller på fastigheten Adils 17 i Borlänge för att öka den ekonomiska lönsamheten. Målet är att uppnå självförsörjning av energiförbrukningen för fastigheten samtidigt som det skall vara ekonomiskt hållbart med återbetalningstid och nettonuvärde i åtanke. Grönfastighetsförädling är något som ligger i tiden för de flesta fastighetsbolagen idag. Flertalet av aktörerna och bolagen på fastighetsmarknaden blir mer och mer medvetna om miljövänliga investeringar och har högt satta miljömål. Där kommer bland annat investeringar i solceller som ett alternativ in vilket idag är något som såväl privatpersoner som kommersiella aktörer antingen redan arbetar med att montera eller strävar mot att investera i. Uppsatsen visat att incitamenten för att arbeta med grön fastighetsförädling för olika aktörer är många. Där de flesta incitamenten är av likartad karaktär även om det finns olikheter för de olika upplåtelseformerna vid grönförädling av befintliga fastigheter. Incitamenten för investeringar i solceller beror till stor del på upplåtelseformerna, vilket uppsatsen påvisar. Det föreligger såklart likheter och skillnader kring incitamenten även för solceller beroende på om det är en bostadsrättsfastighet eller hyresrättsfastighet. Detta utreder och förklara uppsatsen också. För fallstudien beräknades olika alternativa monterings möjligheter på Adils 17 där de mest lönsamma sedan tagits vidare och analyseras ytterligare innan någon slutsats och rekommendation kring montering av solceller på fastigheten har givits. Återbetalningstiderna varierar något beroende på vilket val av montering som väljs, samma gäller för nettonuvärdet. Viktigt är att båda dessa nyckeltal är inom ramen för vad en fastighetsägare likt HSB kan tänka sig för att det skall vara värt att investera, då besparingarna på just denna fastighet från solcellerna tillfaller fastighetsägaren i sin helhet. Två av monterings möjligheterna har i denna uppsats genom fallstudien funnits ligga inom ramen för vad som är en god investering. / The thesis aims to investigate how today's actors work with green property refinement and what different incentives are there for actors to work with this. This is then to analyse in concrete terms what incentives are available for tenant-owner properties and tenant-owner properties to invest in solar cells. What are the similarities and differences between these two forms of lending. The thesis furthermore concretises investments in solar cells in the form of a case study in collaboration with HSB where the financial profitability for the installation of solar cells on the Adils 17 a property in Borlange is carried out. The goal is to achieve self-sufficiency of the energy consumption of the property while being financially sustainable with repayment time and net present value in mind. Green property refinement is something that lays within the time and modern thinking of most real estate companies today. Where most of the actors and companies become more and more aware of environmentally friendly investments and have high environmental goals. There, among other things, investments in solar cells come as an alternative, which today is something that both private individuals and commercial actors are either already working on to assemble or strive to invest in. The thesis has shown that the incentives for working with green property refinement for various actors are many. Where most of the incentives are of a similar character, although there are differences for different forms of tenure in green refinement of existing properties. The incentives for investments in solar cells largely depend on the which form of tenure the property is, as the thesis demonstrates. Of course, there are similarities and differences regarding the incentives for solar cells, depending on whether it is a condominium or rental property. This is also something the thesis will straighten out and explain more in detail. For the case study, various alternative mounting options were calculated on Adils 17 where the most profitable options where further analysed before any conclusion and recommendation regarding the installation of solar cells on the property could be given. The repayment times vary slightly depending on the choice of assembly chosen, the same applies to the net present value. It is important that both of these key figures are within the scope of what a property owner, like HSB MalarDalarna, expects them to be to invest. As the savings on this particular property from the solar cells are due to the property owner. Two of the mounting possibilities in this essay have been calculated to lay within the scope of what could be considered a good investment through the fall study.

[pt] Este trabalho apresenta a caracterização por fotoluminescência de amostras com camadas de arseneto de índio depositadas em substratos de arseneto de gálio. O objetivo é estudar a transição entre os modos bidimensional e tridimensional no crescimento epitaxial em reator MOVPE, com a formação de pontos quânticos autoorganizados pelo método Stranski-Krastanov e a subsequente aplicação da técnica de indium flush. São analisados espectros de fotoluminescência, simulações dos níveis de energia, imagens de microscopia de força atômica e microscopia eletrônica de transmissão para a obtenção de informações sobre densidade, tamanho, uniformidade e energia das transições radiativas dos pontos quânticos. Imagens de microscopia eletrônica de transmissão revelam a qualidade das interfaces e a espessura das camadas. / [en] This work presents the photoluminescence characterization of indium arsenide layers deposited on gallium arsenide substrates. The objective is to analyze the transition in growth mode, from two-dimensional to tri-dimensional in MOVPE, with the formation of self-assembled quantum dots by Stranski-Krastanov method and subsequent use of the indium flush technique. Photoluminescence spectra, quantum well and quantum dot simulations, atomic force microscopy and transmission electron microscopy images are analyzed in order to obtain information about quantum dot size, density, uniformity and electronic transitions. Transmission electron microscopy images reveal the interfaces quality and layers thicknesses.

This master thesis is the last part of the master program Production Engineering and Management at the Royal Institute of Technology, KTH, in Stockholm. The thesis is conducted at Exeger Operations AB, in short Exeger. The company is in an expansion phase and wants to prepare for future production expansion. Thus, a simulation capability to test future production scenarios was desirable. The problem definition was defined by the company together with the authors and led to a literature study within simulation, TPS and Lean manufacturing. Following the literature study, a current state map was produced to achieve sufficient understanding of the production flow at the company. A simulation model was then built. The model was used to test three different ”what-if” scenarios. Buy or Optimize, Future ratio 3:1:1 and Buy or SMED. The authors’ findings in the Buy or Optimize scenario suggest that optimizing the process time in the printers is far better, from multiple perspectives, than investing in new machinery. A 3:1:1 ratio of printers, sinter 1 and assembly station was developed using the simulation model to achieve leveled production flow of these specific processes. Lastly, conducting a SMED on the sinter 1 machine, the setup-,and wait-times achieved a theoretical reduction up to 75 % by altering the SOP and allocating additional preparatory space, in accordance with Lean philosophy. This change would offer the same improvement to a full-scale production as investing in a new sinter 1 according to the simulation model. Future work may consist of Layout Planning and adopting the simulation model to new prerequisites.

Vattenfall Eldistribution AB är en av Sveriges största nätägare och har som mål att få Sverige fossilfritt inom en generation. För att täcka Sveriges elenergibehov på ett fossilfritt sätt krävs det fler förnybara produktionsanläggningar. En av de produktionsanläggningarna som växer mest just nu är solcellsanläggningar. Svenska standarder har regler för hur produktionsanläggningar ska utformas. Det ställs bland annat krav på hur den manuella frånkopplingen ska fungera och att det måste finnas en brytare som kan frånskilja hela produktionsanläggningen, även kallad produktionsbrytare. På grund av olika tolkningar har denna brytare kunnat placeras på olika sätt, men nu vill Vattenfall Eldistribution AB med hjälp av detta arbete ta fram ett standardiserat sätt att placera produktionsbrytaren på. Därför var huvudmålet med arbetet att ta fram riktlinjer för hur kunder till Vattenfall Eldistribution AB ska placera produktionsbrytaren i anläggningen. Arbetet presenterar en övergriplig beskrivning över hur en solcellsanläggning kan se ut samt hur mängden av dessa anläggningar i Sverige har förändrats. Då statistiken visat att antalet produktionsanläggningar ökat varje år blir det allt viktigare att det finns tydligare riktlinjer från nätägare. Dessutom undersöks hur Vattenfall Eldistribution AB behandlar en förfrågan att installera solceller. Genom beräkningar av elnätet avgörs hur anslutningen av produktionsanläggningen kommer att gå till. För att uppnå ett resultat krävdes det att ta in information från flera källor. Vattenfall Eldistribution AB delade med sig av vad som var viktigt för dem och hur de önskar att installationerna är utformade. Som komplement till Vattenfall Eldistribution AB:s yttrande granskades relevanta standarder och föreskrifter. För att ytterligare motivera placeringen till kunder har hänsyn tagits till brandkårens önskemål om solcellsanläggningar. Baserat på informationen från samtliga källor togs riktlinjer fram. Dessa riktlinjer presenterar olika placeringar av produktionsbrytaren. För varje placering beskrivs fördelar och nackdelar. Slutsatserna av arbetet är att produktionsbrytaren behöver placeras utomhus, antingen på byggnadens fasad alternativt i mätarskåpet om det befinner sig utomhus. Utöver placeringen av produktionsbrytaren behöver även växelriktaren till anläggningen uppfylla de krav som ställs av förordningar vilket lättast görs genom att välja en växelriktare som är med i listan ”Rikta Rätt” från Energiföretagen. / Vattenfall Eldistribution AB is one of Sweden's largest grid owners and aims to make Sweden fossil-free within one generation. In order to cover Sweden's electrical energy needs in a fossil-free way, more renewable production plants are required. One of the production plants that is growing the most right now is solar cell plants. Swedish standards have rules for how production plants must be designed. Among other things, there are requirements on how the manual disconnection of the solar cells should work and that there must be a circuit breaker that can disconnect the entire production plant, also called a production circuit breaker. Due to different interpretations, this circuit breaker has been allowed to be placed in different ways, but now Vattenfall Eldistribution AB wants to use this work to develop a standardized way to install the production circuit breaker. Therefore, the main goal of the work has been to produce guidelines for how customers of Vattenfall Eldistribution AB should place the production circuit breaker in the plant. The work presents a comprehensive description of what a solar cell installation might look like and how the amount of these facilities have changed in Sweden. As the statistics show that the number of production facilities increases every year, it is important that there are clearer guidelines from grid owners. In addition, how Vattenfall Eldistribution AB handles a request to install solar panels has been investigated. Through calculations of the electricity network, it is determined how the connection of the production plant will be carried out. In order to achieve a result, it was necessary to gather information from several sources. Vattenfall Eldistribution AB shared what was important to them and how they would like the installations to be designed. As a supplement to Vattenfall Eldistribution AB's opinion, relevant standards and regulations were examined. In order to further justify the placement to customers, consideration was also given to the fire department's requests for solar cell installations. Based on the information from all sources, guidelines were created. These guidelines present different locations of the production circuit breaker. For each location the advantages and disadvantages are described. The conclusions of the work are that the production circuit breaker needs to be placed outdoors, either on the facade of the building or alternatively in the meter cabinet if it is outdoors. In addition to the location of the production circuit breaker, the inverter for the plant also needs to meet the requirements set by regulations, which is done by choosing an inverter that is on the list of "Rikta Rätt" from Swedenergy.

In this thesis, multiple activities have been carried out in order to improve the process of CIGSS solar cell fabrication on a 4" x 4" substrate. The process of CIGSS solar cell fabrication at FSEC's PV Materials Lab involves a series of steps that were all carried out manually in the past. A LABVIEW program has been written to carry out automated sputter deposition of Mo back contact, CuGa, In metallic precursors on a soda lime glass substrate using a stepper motor control for better uniformity. Further, selenization/ sulfurization of these precursors was carried out using rapid thermal processing (RTP). CIGS films were sulfurized using chemical bath deposition (CBD). ZnO:Al was deposited on the CIGSS films using RF sputtering. A separate LABVIEW program was written to automate the process of ZnO:Al deposition. Ni/Al contact fingers were deposited on the ZnO:Al layer using the e-beam evaporation technique. Further, in order to test these solar cells in-house, a simple current-voltage (IV) tracer was fabricated using LABVIEW. A quantum efficiency (QE) measurement setup was built with guidance from the National Renewable Energy Laboratory (NREL). Lastly, analysis of data from photovoltaic (PV) modules installed on the FSEC test site has been carried out using a LABVIEW program in order to find out their rate of degradation as time progresses. A 'C' program has also been written as an aid for keeping a daily log of errors in data and for troubleshooting of the same.

Organic photovoltaics (OPVs) have received a great deal of focus in recent years as a possible alternative to expensive silicon based solar technology. Current challenges for organic photovoltaics are centered around improving their lifetimes and increasing their power conversion efficiencies. One approach to improving the lifetime of such devices has been the inclusion of inorganic metal oxide layers, but interaction between the metal oxides and common conjugated polymers is not favorable. Here we present two methods by which the interactions between polythiophenes and nanostructured ZnO can be made to be more favorable. Using the first method, direct side on attachment of polythiophene to ZnO nanowires via chemical grafting, we demonstrate chemical linkage between the polymer and ZnO phases. The attachment was confirmed to affect the morphological properties of the polymer layer as well, inducing highly ordered regions of the polymer at the ZnO surface via chemical attachment and physical adsorption. Using the second method to improve polythiophene ZnO interactions, we have functionalized ZnO nanowires with organic molecules that favorably interact with conjugated polymer and organic solvents. Photovoltaic devices were made using a blended active layer of functionalized ZnO nanowires and P3HT. Electrical analysis of the resultant devices concluded that the devices were functional photovoltaic cells and isolated the dominant loss mechanisms for further device improvement.