@phdthesis{Zusan2014,
  author    = {Zusan, Andreas},
  title     = {The Effect of Morphology on the Photocurrent Generation in Organic Solar Cells},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-117852},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2014},
  abstract  = {Organic solar cells have great potential to become a low-cost and clean alternative to conventional photovoltaic technologies based on the inorganic bulk material silicon. As a highly promising concept in the field of organic photovoltaics, bulk heterojunction (BHJ) solar cells consist of a mixture of an electron donating and an electron withdrawing component. Their degree of intermixing crucially affects the generation of photocurrent. In this work, the effect of an altered blend morphology on polaron pair dissociation, charge carrier transport, and nongeminate recombination is analyzed by the charge extraction techniques time delayed collection field (TDCF) and open circuit corrected transient charge extraction (OTRACE). Different comparative studies cover a broad range of material systems, including polymer and small-molecule donors in combination with different fullerene acceptors. The field dependence of polaron pair dissociation is analyzed in blends based on the polymer pBTTT-C16, allowing a systematic tuning of the blend morphology by varying the acceptor type and fraction. The effect of both excess photon energy and intercalated phases are minor compared to the influence of excess fullerene, which reduces the field dependence of photogeneration. The study demonstrates that the presence of neat fullerene domains is the major driving force for efficient polaron pair dissociation that is linked to the delocalization of charge carriers. Furthermore, the influence of the processing additive diiodooctane (DIO) is analyzed using the photovoltaic blends PBDTTT-C:PC71BM and PTB7:PC71BM. The study reveals amulti-tiered alteration of the blend morphology of PBDTTT-C based blends upon a systematic increase of the amount of DIO. Domains on the hundred nanometers length scale in the DIO-free blend are identified as neat fullerene agglomerates embedded in an intermixed matrix. With the addition of the additive, 0.6\% and 1\% DIO already substantially reduces the size of these domains until reaching the optimum 3\% DIO mixture, where a 7.1\% power conversion efficiency is obtained. It is brought into connection with the formation of interpenetrating polymer and fullerene phases. Similar to PBDTTT-C, the morphology of DIO-free PTB7:PC71BM blends is characterized by large fullerene domains being decreased in size upon the addition of 3\% DIO. OTRACE measurements reveal a reduced Langevin-type, super-second order recombination in both blends. It is demonstrated that the deviation from bimolecular recombination kinetics cannot be fully attributed to the carrier density dependence of the mobility but is rather related to trapping in segregated PC71BM domains. Finally, with regard to small-molecule donors, a higher yield of photogeneration and balanced transport properties are identified as the dominant factors enhancing the efficiency of vacuum deposited MD376:C60 relative to its solution processed counterpart MD376:PC61BM. The finding is explained by a higher degree of dimerization of the merocyanine dye MD376 and a stronger donor-acceptor interaction at the interface in the case of the vacuum deposited blend.},
  subject      = {Organische Solarzelle},
  language  = {en}
}
@phdthesis{Rauh2013,
  author    = {Rauh, Daniel},
  title     = {Impact of Charge Carrier Density and Trap States on the Open Circuit Voltage and the Polaron Recombination in Organic Solar Cells},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-90083},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2013},
  abstract  = {The focus of this work is studying recombination mechanisms occurring in organic solar cells, as well as their impact on one of their most important parameters — the open circuit voltage Voc. Firstly, the relationship between Voc and the respective charge carrier density n in the active layer under open circuit conditions is analyzed. Therefor, a model after Shockley for the open circuit voltage is used, whose validity is proven with the aid of fits to the measured data. Thereby, it is emphasized that the equation is only valid under special conditions. In the used reference system P3HT:PC61BM the fits are in agreement with the measurement data only in the range of high temperatures (150 - 300 K), where Voc increases linearly with decreasing temperature. At lower temperatures (50 - 150 K), the experiment shows a saturation of Voc. This saturation cannot be explained with the model by the measured falling charge carrier density with decreasing temperatures. In this temperature range Voc is not directly related to the intrinsic properties of the active layer. Voc saturation is due to injection energy barriers at the contacts, which is ascertained by macroscopic simulations. Furthermore, it is observed that Voc in the case of saturation is equivalent to the so-called built-in potential. The difference between the built-in potential and the energy gap corresponds thereby to the sum of the energy barriers at both contacts. With the knowledge of the Voc(n) dependency for not contact limited solar cells, it is possible to investigate the recombination mechanisms of charge carriers in the active layer. For Langevin recombination the recombination rate is Rn2 (recombination order RO = 2), for Shockley-Read-Hall (SRH) Rn1 (RO=1); in various publications RO higher than two is reported with two main explanations. 1: Trap states for charge carriers exist in the respective separated phases, i.e. electrons in the acceptor phase and holes in the donor phase, which leads to a delayed recombination of the charge carriers at the interface of both phases and finally to an apparent recombination order higher than 2. 2: The enhanced R(n) dependency is attributed to the so called recombination prefactor, which again is dependent from n dependent mobility µ. It is shown that for the system P3HT:PC61BM at room temperature the µ(n) dependency does nearly completely explain the higher RO but not at lower temperatures which in this case supports the first explanation. In the material system PTB7:PC71BM the increased RO cannot be explained by the µ(n) dependency even at room temperature. To support the importance of trap states in combination with a phase separation for the explanation of the enhanced RO, additional trap states were incorporated in the solar cells to investigate their influence on the recombination mechanisms. To achieve this, P3HT:PC61BM solar cells were exposed to synthetic air (in the dark and under illumination) or TCNQ was added in small concentrations to the active layer which act as electron traps. For the oxygen degraded solar cell the recombination order is determined by a combination of open Voc-transients and Voc(n) measurements. Thereby, a continuous increase of the recombination order from 2.4 to more than 5 is observed with higher degradation times. By the evaluation of the ideality factor it can be shown that the impact of SRH recombination is increasing with higher trap concentration in relation to Langevin recombination. A similar picture is revealed for solar cells with TCNQ as extrinsic trap states. Finally, a phenomenon called s-shaped IV-curves is investigated, which can sometimes occur for solar cells under illumination. As course of this a reduced surface recombination velocity can be found. Experimentally, the solar cells were fabricated using a special plasma treatment of the ITO contact. The measured IV-curves of such solar cells are reproduced by macroscopic simulations, where the surface recombination velocity is reduced. Hereby, it has to be distinguished between the surface recombination of majority and minority charge carriers at the respective contacts. The theory can be experimentally confirmed by illumination level dependent IV-curves as well as short circuit current density and open circuit voltage transients.},
  subject      = {Organische Solarzelle},
  language  = {en}
}
@phdthesis{Wagenpfahl2013,
  author    = {Wagenpfahl, Alexander Johannes},
  title     = {Numerical simulations on limitations and optimization strategies of organic solar cells},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-90119},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2013},
  abstract  = {Continuously increasing energy prices have considerably influenced the cost of living over the last decades. At the same time increasingly extreme weather conditions, drought-filled summers as well as autumns and winters with heavier rainfall and worsening storms have been reported. These are possibly the harbingers of the expected approaching global climate change. Considering the depletability of fossil energy sources and a rising distrust in nuclear power, investigations into new and innovative renewable energy sources are necessary to prepare for the coming future. In addition to wind, hydro and biomass technologies, electricity generated by the direct conversion of incident sunlight is one of the most promising approaches. Since the syntheses and detailed studies of organic semiconducting polymers and fullerenes were intensified, a new kind of solar cell fabrication became conceivable. In addition to classical vacuum deposition techniques, organic cells were now also able to be processed from a solution, even on flexible substrates like plastic, fabric or paper. An organic solar cell represents a complex electrical device influenced for instance by light interference for charge carrier generation. Also charge carrier recombination and transport mechanisms are important to its performance. In accordance to Coulomb interaction, this results in a specific distribution of the charge carriers and the electric field, which finally yield the measured current-voltage characteristics. Changes of certain parameters result in a complex response in the investigated device due to interactions between the physical processes. Consequently, it is necessary to find a way to generally predict the response of such a device to temperature changes for example. In this work, a numerical, one-dimensional simulation has been developed based on the drift-diffusion equations for electrons, holes and excitons. The generation and recombination rates of the single species are defined according to a detailed balance approach. The Coulomb interaction between the single charge carriers is considered through the Poisson equation. An analytically non-solvable differential equation system is consequently set-up. With numerical approaches, valid solutions describing the macroscopic processes in organic solar cells can be found. An additional optical simulation is used to determine the spatially resolved charge carrier generation rates due to interference. Concepts regarding organic semiconductors and solar cells are introduced in the first part of this work. All chapters are based on previous ones and logically outline the basic physics, device architectures, models of charge carrier generation and recombination as well as the mathematic and numerical approaches to obtain valid simulation results. In the second part, the simulation is used to elaborate issues of current interest in organic solar cell research. This includes a basic understanding of how the open circuit voltage is generated and which processes limit its value. S-shaped current-voltage characteristics are explained assigning finite surface recombination velocities at metal electrodes piling-up local space charges. The power conversion efficiency is identified as a trade-off between charge carrier accumulation and charge extraction. This leads to an optimum of the power conversion efficiency at moderate to high charge carrier mobilities. Differences between recombination rates determined by different interpretations of identical experimental results are assigned to a spatially inhomogeneous recombination, relevant for almost all low mobility semiconductor devices.},
  subject      = {Organische Solarzelle},
  language  = {en}
}
@phdthesis{Foertig2013,
  author    = {F{\"o}rtig, Alexander},
  title     = {Recombination Dynamics in Organic Solar Cells},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-83895},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2013},
  abstract  = {Neben herk{\"o}mmlichen, konventionellen anorganischen Solarzellen — haupts{\"a}chlich auf Silizium basierend — ist die Organische Photovoltaik (OPV) auf dem besten Wege in naher Zukunft eine kosteng{\"u}nstige, umweltfreundliche, komplement{\"a}re Technolgie darzustellen. Die Produktionskosten, die Lebenszeit der Solarzellen sowie deren Wirkungsgrad m{\"u}ssen dabei weiter optimiert werden, um einen Markteintritt der OPV zu erm{\"o}glichen. Die vorliegende Arbeit befasst sich mit der Effizienz organischer Solarzellen und deren Limitierung durch die Rekombination von Ladungstr{\"a}gern. Um funktionsf{\"a}hige Zellen zu untersuchen, werden zeitaufgel{\"o}ste Experimente wie die Messung der transienten Photospannung (TPV), des transienten Photostroms (TPC), die Ladungsextraktion (CE) sowie die time delayed collection field (TDCF) Methode angewandt. Untersucht werden sowohl fl{\"u}ssig prozessierte als auch aufgedampfte Proben, unterschiedliche Materialzusammensetzungen und verschiedene Probengeometrien. Das Standardmaterialsystem der OPV, P3HT:PC61BM, wird bei verschiedenen emperaturen und Beleuchtungsst{\"a}rken auf die Lebenszeit und Dichte der photogenerierten Ladungstr{\"a}ger {\"u}berpr{\"u}ft. F{\"u}r den Fall spannungsunabh{\"a}ngiger Generation von Ladungstr{\"a}gern zeigt sich die Anwendbarkeit der Shockley-Gleichung auf organische Solarzellen. Des Weiteren wird ein konsistentes Modell erl{\"a}utert, welches den Idealtit{\"a}tsfaktor direkt mit der Rekombination von freien mit gefangenen, exponentiell verteilten Ladungstr{\"a}gern verkn{\"u}pft. Ein Ansatz, bekannt unter der Bezeichung j=V Rekonstruktion, erm{\"o}glicht es, den leistungslimitierenden Verlustmechanismus in unbehandelten und thermisch geheizten P3HT:PC61BM Solarzellen zu identifizieren. Dieses Verf ahren, welches TPV, CE und TDCF Messungen beinhaltet, wird auf Proben basierend auf dem neuartigen, low-band gap Polymer PTB7 in Verbindung mit dem Fulleren PC71BM ausgeweitet. W{\"a}hrend in der Zelle hergestellt aus reinem Chlorbenzol betr{\"a}chtliche geminale wie nichtgeminale Verluste zu beobachten sind, erleichtert die Zugabe eines L{\"o}sungsmittelzusatzes die Polaronenpaartrennung, was zu einer starken Reduktion geminaler Verluste f{\"u}hrt. In einer Kooperation mit dem IMEC Institut in Leuven, werden abschließend die beiden bedeutensten Probenarchitekturen organischer Solarzellen, die planare und die Misch{\"u}bergang Struktur, jeweils basierend auf CuPC und C60, bez{\"u}glich nichtgeminaler Rekombination und Ladungstr{\"a}gerverteilung miteinander verglichen. Neben den beiden experimentellen Techniken um TPV und CE werden makroskopische Simulationen herangezogen, um den Ursprung unterschiedlichen Voc vs. Lichtintensit{\"a}t-Verhaltens zu erkl{\"a}ren.},
  subject      = {Organische Solarzelle},
  language  = {en}
}
@phdthesis{Mingebach2012,
  author    = {Mingebach, Markus Harald},
  title     = {Photocurrent in Organic Solar Cells},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-73569},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2012},
  abstract  = {A quite new approach to low-cost mass production of flexible solar cells are organic photovoltaics. Even though the device efficiencies increased rapidly during the last years, further imporvements are essential for a successful market launch. One important factor influencing the device efficiency is the photocurrent of a solar cell, which is defined as the difference between the current under illumination and in the dark. In case of organic bulk heterojunction (BHJ) solar cells it is — in contrast to inorganic devices — dependent on the applied bias voltage. The voltage dependence results in a reduced fill factor and thus an even more pronounced influence of the photocurrent on the device efficiency. It is therefore crucial to understand the underlying processes determining the photocurrent in order to be able to further improve the solar cell performance. In a first step the photocurrent of P3HT:PC61BM devices was investigated by a pulsed measurement technique in order to prevent disturbing influences due to device heating under continous illumination. The resulting photocurrent was hyperbolic tangent like and featured a point symmetry, whose origin and meaning were discussed. In addition, the photocurrent was described by a combined model of Braun-Onsager and Sokel-Hughes theory for field dependent polaron pair dissociation and charge extraction, respectively. After this macroscopic view on the photocurrent, the focus of this work moves to the more basic processes determining the photocurrent: charge photogeneration and recombination. In a comparative study the field-dependence of these was investigated by time-delayed collection field (TDCF) measurements for two well-known reference systems, namely P3HT:PC61BM and MDMO-PPV:PC61BM. It was possible to identify two different dominating scenarios for the generation of free charge carriers. The first one — via a thermalized charge transfer state (CTS) — is clearly influenced by geminate recombination and therefore less efficient. In the second scenario, the free charge carriers are either generated directly or via an excited, "hot" CTS. In addition, clear differences in the nongeminate recombination dynamics of both material systems were found. Similar studies were also be presented with two modern low bandgap polymers which only differ by the bridging atom in the cyclopentadithiophene (PCPDTBT:PC71BM vs. Si-PCPDTBT:PC71BM). Such small changes in the chemical structure were already sufficient to affect the charge photogeneration as well as the morphology of the blend. These findings were set into relation to current-voltage characteristics in order to discuss the origin of the clear differences in the solar cell performance of both materials. Another crucial parameter limiting the solar cell efficiency is the builtin potential of a device. Within the range of semiconducting pn-junctions, Mott-Schottky analysis is an established method to determine the built-in potential. As it was originally derived for abrupt pn-junctions, its validity for organic BHJ solar cells — a bipolar, effective medium — was discussed. Experimental findings as well as the contradictions to Mott-Schottky theory indicated, that a direct transfer of this method to organic photovoltaics is not appropriate. Finally, the results obtained in the framework of the MOPS-project (Massengedruckte Organische Papier-Solarzellen) will be presented, in which the first completely roll-to-roll printed paper solar cells were realized.},
  subject      = {Organische Solarzelle},
  language  = {en}
}
@phdthesis{Baumann2011,
  author    = {Baumann, Andreas},
  title     = {Charge Transport and Recombination Dynamics in Organic Bulk Heterojunction Solar Cells},
  url       = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-64915},
  school      = {Universit{\"a}t W{\"u}rzburg},
  year      = {2011},
  abstract  = {The charge transport in disordered organic bulk heterojunction (BHJ) solar cells is a crucial process affecting the power conversion efficiency (PCE) of the solar cell. With the need of synthesizing new materials for improving the power conversion efficiency of those cells it is important to study not only the photophysical but also the electrical properties of the new material classes. Thereby, the experimental techniques need to be applicable to operating solar cells. In this work, the conventional methods of transient photoconductivity (also known as "Time-of-Flight" (TOF)), as well as the transient charge extraction technique of "Charge Carrier Extraction by Linearly Increasing Voltage" (CELIV) are performed on different organic blend compositions. Especially with the latter it is feasible to study the dynamics, i.e. charge transport and charge carrier recombination, in bulk heterojunction (BHJ) solar cells with active layer thicknesses of 100-200 nm. For a well performing organic BHJ solar cells the morphology is the most crucial parameter finding a trade-off between an efficient photogeneration of charge carriers and the transport of the latter to the electrodes. Besides the morphology, the nature of energetic disorder of the active material blend and its influence on the dynamics are discussed extensively in this work. Thereby, the material system of poly(3-hexylthiophene-2,5-diyl) (P3HT) and [6,6]-phenyl-C61 butyric acid methyl ester (PC61BM) serves mainly as a reference material system. New promising donor or acceptor materials and their potential for application in organic photovoltaics are studied in view of charge dynamics and compared with the reference system. With the need for commercialization of organic solar cells the question of the impact of environmental conditions on the PCE of the solar cells raises. In this work, organic BHJ solar cells exposed to synthetic air for finite duration are studied in view of the charge carrier transport and recombination dynamics. Finally, within the framework of this work the technique of photo-CELIV is improved. With the modified technique it is now feasible to study the mobility and lifetime of charge carriers in organic solar cells under operating conditions.},
  subject      = {Photovoltaik},
  language  = {en}
}