iv ABSTRACT OPTIMIZATION OF METALIZATION IN CRYSTALLINE SILICON SOLAR CELLS Demircioglu, Olgu M. Sc. Department of Micro and Nanotechnology Supervisor : Prof. Dr. Rasit Turan Co-Supervisor : Assist. Prof. Dr. H. Emrah &Uuml / nalan August 2012, 103 pages Production steps of crystalline silicon solar cells include several physical and chemical processes like etching, doping, annealing, nitride coating, metallization and firing of the metal contacts. Among these processes, the metallization plays a crucial role in the energy conversion performance of the cell. The quality of the metal layers used on the back and the front surface of the cell and the quality of the electrical contact they form with the underlying substrate have a detrimental effect on the amount of the power generated by the cell. All aspects of the metal layer, such as electrical resistivity, contact resistance, thickness, height and width of the finger layers need to be optimized very carefully for a successful solar cell operation. In this thesis, metallization steps within the crystalline silicon solar cell production were studied in the laboratories of Center for Solar Energy Research and Application (G&Uuml / NAM). Screen Printing method, which is the most common metallization technique in the industry, was used for the metal layer formation. With the exception of the initial experiments, 6

The energy crisis and environmental consciousness arising in recent years induce the rapid development of renewable energy technology, especially in solar energy field. Under the policy support of Germany and Japan, the solar energy market expands to the world speedily. Moreover, due to the high values of environmental protection topics in United Nations and European Union and Kyoto Protocol establishment, the renewable energy industry is imperative to prevail among the world. As a result of the industrial rapid growth, companies adopt all kinds of tactics to develop capability in order to occupy the renewable energy market. Thanks to the remarkable achievement in LCD-TFT and semiconductor industries, Taiwan manufacturers applied the past experiences to invest in the solar cell industry, especially in thin film solar cell product. During 2005 to 2007, many companies found one after another. This research mainly probes into the trend of Taiwan thin film solar cell industry. First, understand the competitors and global market conditions, then penetrate the industrial structure with Porter¡¦s five forces model, discuss the competitive advantage of Taiwan with Porter¡¦s diamond model, and look for the competitive ability of Taiwan thin film solar cell industry by SWOT analysis. Finally, the research proposes some developing suggestions for Taiwan thin film solar cell industry.

With the raise of nanotechnology researching, many special physical and chemical properties were found gradually in nanoscale. Among them, the one-dimension nanostructure owns high specific surface area and excellent electron emission properties. Moreover, the two-dimension arrayed nanostructure has the characteristics of photonic crystal and moth-eye effect. Currently, advanced lithographic methods such as electron beam (E-beam) or deep ultraviolet (DUV) lithography and X-ray lithography are adopted to define periodic nanoscale patterns. But these lithographic equipment are too expensive. Moreover, costly etching methods such as inductively coupled plasma reactive ion etching (ICP-RIE) or electron cyclotron resonance reactive ion etching (ECR-RIE) must be used to form arrayed silicon nanostructure with high aspect ratios. The nanoscale array patterns can be defined on the surface of the silicon wafer by the self-assembly of a polystyrene nanosphere. The photo-assisted electrochemical etching (PAECE) has the advantage of forming nanopore, and the aspect ratio of etched nanopores can be as high as 50:1 which is better than ICP-RIE. Therefore, PAECE is very suitable to fabricate nanostructure. This high-cost drawback makes most of academias and small/medium enterprises hard to invest in nanotechnology. This study combines the self-assembly nanosphere lithography (SANSL) process and photo-assisted electrochemical etching to fabricate a nanostructure array with a high aspect ratio on the surface of a silicon wafer. Experimental results show that the nanosphere array with a nearly perfect arrangement can be obtained in the sample of 1.8 ∗1.8 cm2 by spin coating and vibration coating. Using reactive ion etching (RIE) can transfer the nanosphere array pattern to the silicon nitride layer, and form the etching window of PAECE. The concentration of the HF electrolyte used in PAECE was 2.5 wt%. When PAECE was performed with etching mask can produce deeper and periodic nanopores. The surfactant of SDSS added in the HF electrolyte of PAECE can reduce the contact angle of electrolyte and avoid the phenomenon of hole-reaming. When the voltage of 1 V is used to etch for 12.5 min, the etching depth of the nanopore array structure is about 5.69 £gm and its diameter is about 90 nm, such that the aspect ratio of the pore can reach about 63:1. If the etching voltage was increased, the width of pore will be increased and the depth of pore will be reduced gradually at the same time. When the etching voltage of 2 V is applied to etch for 5 min, the etching height of the nanopillar is about 2 £gm and its diameter is about 100 nm, such that the aspect ratio of the pillar can reach about 20:1. The nanopillar was arranged periodically according to the definition of nanosphere, therefore the arrayed nanopillar can be realized successfully. Dropping the solution which has biological samples into the gap of nanopillar, it will affect the light which goes through the nanostructure and produce specific parameters of polarization. The results showed that when the DI water was dropped into the nanopillar structure, the degree of polarization (DOP) is 0.981, azimuth is 4.86¢X and ellipticity is 2.83¢X. When the solution which has alkaline lysis plasmid of 5 £gg/ml was dropped into the nanopillar structure, the DOP is 0.957, azimuth is 7.7¢X and ellipticity is 3.99¢X. The result shows that the change of polarization parameter has the relations with the concentration of biological samples in solution. Therefore, the measure system can be combined with nanopillar array to develop the photonic crystal biosensor. This study also applies the developed nanopore nanostructure array to fabricate sub-wavelength antireflection structure of solar cell. Experimental results show that the deeper in structure and then the better in antireflective effect. After performing 1 V PAECE for 5 min, the weighted mean reflectance can be reduced to 1.73% under the wavelength range of 280¡V890 nm. Further coating of a silicon nitride layer on the surface of a nanostructure array reduces the weighted mean reflectance even to 0.878 %. Finally, this study also uses various voltage of PAECE to produce nanostructure array with different surface area for the electrode fabrication of fuel cell. Experimental results show that the larger in surface area of sample and then the better in catalysis effect. Two-staged PAECE of 1.5 V and 1.75 V can yield nanopillar with surface area of 14.2 cm2 , which is about 50.2 times higher than a planar electrode. When the surface of such a nanopillar array is coated with platinum of 1000 Å, the reaction current of nanopillar array is 10.2 mA, which is 72.9 times higher than that obtained by only a planar electrode.

Though relatively young, the field of organic electronics is a rapidly growing market and considerable research is being done in creating a whole range of devices from organic molecules from organic field effect transistors to LEDs to photovoltaic devices. The field of organic photovoltaic in particular has become important in recent years with the push for newer, renewable sources of energy to end the dependence on fossil fuels. While the efficiencies of organic photovoltaic devices continue to rise, one barrier to their commercial adoption has been the limited lifetimes of these devices. While certain degradation methods of organic photovoltaics, such as photo-oxidation, have been extensively studied and solutions to these problems, such as encapsulation, are being researched, certain other degradation mechanisms are less understood and studied. The focus of this thesis is on one such degradation mechanism, UV degradation, specific to the ITO-pentacene interface in pentacene/C60 organic photovoltaic devices. Attempts were made to increase the lifetime of the devices by using phosphonic acids or oxygen plasma to modify the surface of the ITO. While conducting these experiments, the lack of a system to test the lifetime of multiple devices for long periods of time became apparent. As such as system was a requirement for future research into the lifetimes of organic photovoltaic devices a system was designed and built. The system would operate the photovoltaic device in a way comparable to its end-use and would allow over 100 devices to be tested simultaneously for durations exceeding 10,000 hours if necessary. This system would allow for statistically significant lifetime testing to be carried out in the future.

Organische Solarzellen besitzen das Potential für leichte und zugleich flexible photovoltaische Anwendungen, die kostengünstig hergestellt werden können und damit einen Beitrag zur Verminderung der Emission von Kohlendioxid, Methan und Stickoxiden leisten können. Zur Herstellung von organischen Solarzellen werden nur geringe Mengen der organischen Materialien benötigt und die Prozessierung findet bei vergleichsweise geringen Temperaturen statt, was die Abscheidung auf z. B. Plastikfolie ermöglicht. Man unterscheidet drei Arten von organischen Solarzellen. Erstens, Solarzellen bestehend aus kleinen Molekülen, die im Vakuum durch Sublimation auf das Substrat abgeschieden werden. Zweitens, Polymersolarzellen, deren Schichten aus Lösung meist durch „spin-coating“ oder Druckverfahren präpariert werden. Und drittens, „dye-sensitized“ Solarzellen (auch Grätzel-Zellen), die aus einer porösen Schicht Titandioxid und einem flüssigen Elektrolyten für den Ladungsträgertransport bestehen. Diese Arbeit beschäftigt sich ausschließlich mit organischen Solarzellen aus kleinen Molekülen. Die höchsten erreichten Wirkungsgrade organischer Solarzellen aus kleinen Molekülen liegen derzeit bei etwa 5 % . Um die Effizienzen von Solarzellen aus kleinen Molekülen zu steigern, ist es einerseits notwendig das Verständnis der physikalischen und chemischen Prozesse innerhalb der Bauelemente genauer beschreiben zu können, andererseits werden neue Materialien mit optimierten Eigenschaften für die organische Photovoltaik benötigt. In dieser Arbeit wurden zwei Strategien zur Optimierung organischer Solarzellen verfolgt: • Durch die Optimierung des Versatzes der Energieniveaus der organischen Materialien konnte die Leerlaufspannung in einem Modellsystem maximiert werden. An diesem Modellsystem wurden der Ursprung der Leerlaufspannung und die Rekombinationsdynamik von photogenerierten Ladungsträgern untersucht. Bezüglich der Leerlaufspannung zeigen Solarzellen, deren photoaktive Materialien in einer Mischschicht vorliegen, im Vergleich zu Solarzellen, die eine photoaktive Doppelschicht beinhalten, fundamentale Unterschiede . • Des Weiteren wurden neue Thiophenderivate untersucht, die als aktive Materialien in organischen Solarzellen eingesetzt wurden. Durch elektronenziehende Endgruppen wurde das Ionisationspotential der Thiophenderivate abgesenkt und die optische Bandlücke verringert. Das Thiophenderivat DCV3T fungiert in Kombination mit herkömmlichen Donator-Materialien als Akzeptor. In Mischschichten aus DCV3T und C60 kommt es durch einen Hin- und Rücktransfer der Anregungsenergie zwischen den Materialien statt der Generation von freien Ladungsträgern zu einer Erhöhung der Triplett-Exzitonendichte auf DCV3T . Diese Exzitonen besitzen auf Grund der hohen Lebensdauer von Triplett-Exzitonen das Potential für eine erhöhte Exzitonendiffusionslänge, die in einem neuen Solarzellenkonzept ausgenutzt werden konnte . / Organic solar cells have the potential for light weight and flexible applications. They can be manufactured cost-effectively and can thus contribute to the reduction of the emission of carbon dioxide, methane and nitric oxides. In order to manufacture organic solar cells, only small amounts of organic materials are required. They can be processed at comparably low temperatures. Therefore, the fabrication on substrates like plastic foil is possible. Three different types of organic solar cells exist. The first kinds are solar cells prepared from small molecules that are manufactured via sublimation of the material in a vacuum. The second kind are polymer solar cells manufactured from solution by spin coating techniques or ink jet printing. And thirdly, dye sensitized solar cells - also known as Grätzel cells - consisting of a porous layer of titanium dioxide and most commonly a liquid electrolyte for the charge transport. This work deals exclusively with small molecule solar cells. The highest power conversion efficiencies reached by small molecule organic photovoltaics are now in the range of 5 %. In order to increase the efficiencies of solar cells prepared from small molecules, two major aspects must be developed. The understanding of the physical processes within the organic devices must be improved. And secondly, new materials are required with physical properties optimized for organic photovoltaics. In this work, I followed two strategies for optimizing organic solar cells: • By optimizing the offset of energy levels between donor and acceptor material, the open circuit voltage could be increased. In the investigated model system, the origin of the open circuit voltage and the recombination dynamics of photo generated charge carriers were analyzed. Concerning the open circuit voltage, solar cells consisting of a donor acceptor double layer structure, show fundamental differences to solar cells consisting of a donor acceptor blend. • Furthermore, new thiophene derivatives used as photoactive materials were investigated. By the attachment of electron withdrawing end groups, the ionization potential of the oligothiophenes is increased and the optical band gap is reduced at the same time. The investigated thiophene derivative DCV3T acts as an acceptor in combination with the commonly used donor-materials. A back- and forth-transfer of excitation energy is observed in blends of DCV3T and fullerene C60. In these blends, excitons are not separated into free charge carriers. This back and forth transfer leads to an enhancement of the density of triplet excitons on DCV3T. These excitons have a potentially high diffusion length due to the long lifetime of triplet excitons. This effect was utilized in the organic solar cells.

Organic solar cells promise electricity generation at very low cost, and higher installation flexibility as compared to inorganic solar cells. The lower cost is achieved by cheaper semiconductors and easier manufacturing processes. The flexibility is naturally given by these ultra-thin, amorphous layers. Also the power conversion efficiency can be high enough for many applications. The organic molecules have to withstand the constant excitation by photons, transport of energy in form of excitons and charge. A small but significant amount of these photons has energy over the absorption gap, the excess of energy must be released without breaking the molecular bonds. In consequence, the solar cells can also heat up to temperatures at above 80°C. The objective of this work is to answer the question if the small molecules organic solar cells can be stable enough to operate under a very long time. The stability of organic doped layers in an organic solar cell is also addressed. This work starts with a general introduction followed by the description of the experimental procedures. The aging experiments of the solar cell were done with a self developed equipment. The fabrication of this equipment (a set of measurement boxes) was necessary to maintain the conditions, under which a solar cell can be aged, as constant as possible. The measurement boxes were used to control the electrical load of the cell, its temperature, the illumination intensity, and its electric connection to the IxV measurement equipment. A software package was also developed to control the equipment and to facilitate the work and visualization of the high volume of collected data. The model solar cells chosen for the aging experiments were donor-acceptor heterojunctions devices formed with the well-known materials C60 and ZnPc. Two basic different structures were analyzed, because they offered reasonable performance and potentially long lifetime: the flat heterojunction (FHJ) and the mixed heterojunction in a Metal-Insulator-p-Semiconductor (m-i-p) configuration. Variations of the FHJ and of the m-i-p structures are also used to verify the limits of the stability of electrically p- and n- doped organic semiconducting layers. The least stable solar cells are the FHJ devices. These devices show a fast initial decrease of all their characteristic conversion parameters but the Voc. After a few hundred hours, the saturation current (current under a reverse bias of 1 V) was almost stable. The saturation current is related to the number of absorbing centers, the decrease indicates that the degradation of the absorbing centers has stopped. With wavelength resolved external quantum efficiency measurements and chemical analysis, it was found that the degradation is related to the oxidation of C60. It was also shown that the use of organic dopants do not significantly affect the lifetime. The results show that the m-i-p solar cells are more stable than the FHJ devices. They are also stable under high temperatures up to 105°C. Outdoor testing also showed that the solar cells remained chemically, electrically and mechanically stable during a 900 h test.

<p>Organic solar cells have caught considerable attention in the past few years due to their potential for providing environmentally safe, flexible, lightweight, inexpensive, and roll-to-roll feasible production solar cells. However, the efficiency achieved in current organic solar cells is quite low, yet quick and successive improvements render it as a promising alternative. A hopeful approach to improve the efficiency is by exploiting the tandem concept which consists of stacking two or more organic solar cells in series.</p><p>One important constituent in tandem solar cells is the middle electrode layer which is transparent and functions as a cathode for the first cell and an anode for the second cell. Most studies done so far have employed noble metals such as gold or silver as the middle electrode layer; however, they suffered from several shortcomings especially with respect to reproducibility.</p><p>This thesis focuses on studying a new trend which employs an oxide material based on nano-particles as a transparent cathode (such as Zinc-oxide-nano-particles) along with a transparent anode so as to replace the middle electrode.</p><p>Thus, this work presents a study on solution processable zinc oxide (ZnO) nanostructures, their proper handling techniques, and their potential as a middle electrode material in Tandem solar cells in many different configurations involving both polymer and small molecule materials. Moreover, the ZnO-np potential as a candidate for acceptor material is also investigated.</p>

<p>This project is an extension of a pre-existing simulation program (‘Simulation_2dioden’). This simulation program was first developed in Konarka Technologies. The main purpose of the project ‘Simulation_2dioden’ is to calibrate the values of different parameters like, Shunt resistance, Series resistance, Ideality factor, Diode current, epsilon, tau, contact probability, AbsCT, intensity, etc; This is one of the curve fitting procedure’s. This calibration is done by using different equations. Diode equation is one of the main equation’s used in calculating different currents and voltages, from the values generated by diode equation all the other parameters are calculated.</p><p>The reason for designing this simulation_2dioden is to calculate the values of different parameters of a device and the researcher would know which parameter effects more in the device efficiency, accordingly they change the composition of the materials used in the device to acquire a better efficiency. The platform used to design this project is ‘Microsoft Excel’, and the tool used to design the program is ‘Visual basics’. The program could be otherwise called as a ‘Virtual Solar cell’. The whole Virtual Solar cell is programmed in a single excel sheet.</p><p>An Automated working solution is suggested which could save a lot of time for the researchers, which is the main aim of this project. To calibrate the parameter values, one has to load the J-V characteristics and simulate the program by just clicking one button. And the parameters extracted by using this automated simulation are Parallel resistance, Series resistance, Diode ideality, Saturation current, Contact properties, and Charge carrier mobility.</p><p>Finally, a basic working solution has been initiated by automating the simulation program for calibrating the parameter values.</p>

Ce travail traite de la croissance épitaxiale et de la caractérisation d’hétérostructures àbase de multi-puits quantiques (MPQ) pour des applications dans le photovoltaïque. Leséchantillons ont été obtenus par la technique d’épitaxie en phase vapeur aux organométalliques(EPVOM) sur des substrats de saphir (0001). La caractérisation structurale etoptique est réalisée par diffraction de rayons X, microscopie électronique en transmission,spectroscopie de photoluminescence et de transmission. Pour étudier la présence de l’effetphotovoltaïque et pour estimer la performance électrique des échantillons, les MPQ ont étéintégrés dans la géométrie de cellules solaires en utilisant de la photolithographie, desattaques réactives ioniques assistées par plasma inductif et des métallisations pour contacterles parties dopées n et p.Nous avons étudié l’influence de différents designs des régions actives InGaN/GaN surles propriétés optiques et électriques des échantillons, c’est-à-dire le nombre de puitsquantiques InGaN, les épaisseurs des puits et des barrières et la composition en indium dansles puits. Deux mécanismes principaux doivent être pris en compte pour une optimisationefficace de composants photovoltaïques: l’absorption des photons et la collections desporteurs. Nous avons montré qu’une augmentation du nombre de MPQ, de leur épaisseur etde la composition d’In améliorait l’absorption, mais causait aussi des pertes dans l’efficacitéde collection du fait de l’augmentation de l’épaisseur de la couche active (champ électriqueplus faible), de la difficulté des porteurs pour s’échapper de puits plus profonds et derelaxation des contraintes (création de défauts structuraux). La décroissance de l’épaisseur desbarrières peut résoudre les deux premiers points, mais le problème de la relaxation de lacontrainte reste entier. Pour notre meilleur design, nous obtenons une efficacité de conversionde 2 % pour des couches 15×In0.18Ga0.82N/GaN qui ont une réponse spectrale qui s’étendjusqu’à 465 nm. / In this work we report on epitaxial growth and characterization of InGaN/GaN multiquantumwells (MQWs) heterostructures for application in photovoltaic devices. The sampleswere grown by metal-organic vapor phase epitaxy (MOVPE) on (0001) sapphire substrate.The structural and optical characterization is performed by X-ray diffraction, transmissionelectron microscopy, photoluminescence spectroscopy and transmission measurements. Toinvestigate the presence of photovoltaic effect and estimate the electrical performance of thesamples, they were processed into solar cells by means of the photolithography, inductivelycoupled plasma reactive-ion etching and metallization to manage n and p contacts.We studied the influence of different InGaN/GaN active region designs on thestructural, optical and electrical properties of the samples, i.e. number of InGaN quantumwells, QW and quantum barrier thicknesses and indium composition in the wells. Two mainmechanisms have to be taken into account for an efficient optimization of photovoltaicdevices: photon absorption and carrier collection. We showed that an increase of the MQWsnumber, their thickness and the In-content allows absorption improvement, but causes lossesin the carrier collection efficiency due to: the increase of the active region thickness (lowerelectric field), the difficulty of the carrier to escape from deeper QWs and the strain relaxation(structural defect creation). The decrease of the barrier thickness can solve the first two issues,but the problem with strain relaxation remains. In the best design, we report the value of2.00% of conversion efficiency for 15×In0.18Ga0.82N/GaN samples with spectral responseextending to 465 nm.

In this dissertation, the multiple facets of benzodithiophene (BDT) units are explored, with a focus on understanding how the isomerism of the BDT structure affects the macroscopic properties of the oligomeric and polymeric materials created. First, the story focuses on an overview of the BDT synthons and their applications in organic electronics. A straightforward synthesis of BDT and its derivatization to seven π-conjugated building blocks and seven polymers is presented. Then, symmetric (donor)2-acceptor (D2-A) dye architecture for application in dye-sensitized solar cells are investigated. Two isomeric systems are studied, and the branched sensitizers show a greater incident photon-to-current efficiency than the linear dyes. The nature of the accepting core is also varied between dibenzophenazine to dithienophenazine. The sensitizer with the weakest accepting core displays the best photovoltaic performance, due to an increase in the open-circuit voltage of ~100 mV caused by the favorable shift of the metal oxide conduction band. Lastly, a study of the donating building blocks in these (D2-A) sensitizers demonstrates that increasing the number of donor units from two to six thiophene moiety doubles the solar cell performance, due to the improvement of the light harvesting ability.