TY - JOUR A1 - Ran, Niva A. A1 - Love, John A. A1 - Heiber, Michael C. A1 - Jiao, Xuechen A1 - Hughes, Michael P. A1 - Karki, Akchheta A1 - Wang, Ming A1 - Brus, Viktor V. A1 - Wang, Hengbin A1 - Neher, Dieter A1 - Ade, Harald A1 - Bazan, Guillermo C. A1 - Thuc-Quyen Nguyen, T1 - Charge generation and recombination in an organic solar cell with low energetic offsets JF - dvanced energy materials N2 - Organic bulk heterojunction (BHJ) solar cells require energetic offsets between the donor and acceptor to obtain high short-circuit currents (J(SC)) and fill factors (FF). However, it is necessary to reduce the energetic offsets to achieve high open-circuit voltages (V-OC). Recently, reports have highlighted BHJ blends that are pushing at the accepted limits of energetic offsets necessary for high efficiency. Unfortunately, most of these BHJs have modest FF values. How the energetic offset impacts the solar cell characteristics thus remains poorly understood. Here, a comprehensive characterization of the losses in a polymer:fullerene BHJ blend, PIPCP:phenyl-C61-butyric acid methyl ester (PC61BM), that achieves a high V-OC (0.9 V) with very low energy losses (E-loss = 0.52 eV) from the energy of absorbed photons, a respectable J(SC) (13 mA cm(-2)), but a limited FF (54%) is reported. Despite the low energetic offset, the system does not suffer from field-dependent generation and instead it is characterized by very fast nongeminate recombination and the presence of shallow traps. The charge-carrier losses are attributed to suboptimal morphology due to high miscibility between PIPCP and PC61BM. These results hold promise that given the appropriate morphology, the J(SC), V-OC, and FF can all be improved, even with very low energetic offsets. KW - energetic offset KW - fill factor KW - morphology KW - organic solar cells KW - recombination Y1 - 2018 U6 - https://doi.org/10.1002/aenm.201701073 SN - 1614-6832 SN - 1614-6840 VL - 8 IS - 5 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Love, John A. A1 - Chou, Shu-Hua A1 - Huang, Ye A1 - Bazan, Guillermo C. A1 - Thuc-Quyen Nguyen, T1 - Effects of solvent additive on "s-shaped" curves in solution-processed small molecule solar cells JF - Beilstein journal of organic chemistry N2 - A novel molecular chromophore, p-SIDT(FBTThCA8)(2), is introduced as an electron-donor material for bulk heterojunction (BHJ) solar cells with broad absorption and near ideal energy levels for the use in combination with common acceptor materials. It is found that films cast from chlorobenzene yield devices with strongly s-shaped current-voltage curves, drastically limiting performance. We find that addition of the common solvent additive diiodooctane, in addition to facilitating crystallization, leads to improved vertical phase separation. This yields much better performing devices, with improved curve shape, demonstrating the importance of morphology control in BHJ devices and improving the understanding of the role of solvent additives. KW - current voltage analysis KW - morphology KW - organic solar cells Y1 - 2016 U6 - https://doi.org/10.3762/bjoc.12.249 SN - 1860-5397 VL - 12 SP - 2543 EP - 2555 PB - Beilstein-Institut zur Förderung der Chemischen Wissenschaften CY - Frankfurt, Main ER - TY - JOUR A1 - Albrecht, Steve A1 - Vandewal, Koen A1 - Tumbleston, John R. A1 - Fischer, Florian S. U. A1 - Douglas, Jessica D. A1 - Frechet, Jean M. J. A1 - Ludwigs, Sabine A1 - Ade, Harald W. A1 - Salleo, Alberto A1 - Neher, Dieter T1 - On the efficiency of charge transfer state splitting in polymer: Fullerene solar cells JF - Advanced materials KW - organic solar cells KW - charge generation KW - geminate recombination KW - charge transfer states KW - driving force KW - excess energy KW - morphology KW - spectroelectrochemistry Y1 - 2014 U6 - https://doi.org/10.1002/adma.201305283 SN - 0935-9648 SN - 1521-4095 VL - 26 IS - 16 SP - 2533 EP - 2539 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Pingel, Patrick T1 - Morphology, charge transport properties, and molecular doping of thiophene-based organic semiconducting thin films T1 - Morphologie, Ladungstransporteigenschaften und molekulares Dotieren thiophenbasierter organischer Halbleiterschichten N2 - Organic semiconductors combine the benefits of organic materials, i.e., low-cost production, mechanical flexibility, lightweight, and robustness, with the fundamental semiconductor properties light absorption, emission, and electrical conductivity. This class of material has several advantages over conventional inorganic semiconductors that have led, for instance, to the commercialization of organic light-emitting diodes which can nowadays be found in the displays of TVs and smartphones. Moreover, organic semiconductors will possibly lead to new electronic applications which rely on the unique mechanical and electrical properties of these materials. In order to push the development and the success of organic semiconductors forward, it is essential to understand the fundamental processes in these materials. This thesis concentrates on understanding how the charge transport in thiophene-based semiconductor layers depends on the layer morphology and how the charge transport properties can be intentionally modified by doping these layers with a strong electron acceptor. By means of optical spectroscopy, the layer morphologies of poly(3-hexylthiophene), P3HT, P3HT-fullerene bulk heterojunction blends, and oligomeric polyquaterthiophene, oligo-PQT-12, are studied as a function of temperature, molecular weight, and processing conditions. The analyses rely on the decomposition of the absorption contributions from the ordered and the disordered parts of the layers. The ordered-phase spectra are analyzed using Spano’s model. It is figured out that the fraction of aggregated chains and the interconnectivity of these domains is fundamental to a high charge carrier mobility. In P3HT layers, such structures can be grown with high-molecular weight, long P3HT chains. Low and medium molecular weight P3HT layers do also contain a significant amount of chain aggregates with high intragrain mobility; however, intergranular connectivity and, therefore, efficient macroscopic charge transport are absent. In P3HT-fullerene blend layers, a highly crystalline morphology that favors the hole transport and the solar cell efficiency can be induced by annealing procedures and the choice of a high-boiling point processing solvent. Based on scanning near-field and polarization optical microscopy, the morphology of oligo-PQT-12 layers is found to be highly crystalline which explains the rather high field-effect mobility in this material as compared to low molecular weight polythiophene fractions. On the other hand, crystalline dislocations and grain boundaries are identified which clearly limit the charge carrier mobility in oligo-PQT-12 layers. The charge transport properties of organic semiconductors can be widely tuned by molecular doping. Indeed, molecular doping is a key to highly efficient organic light-emitting diodes and solar cells. Despite this vital role, it is still not understood how mobile charge carriers are induced into the bulk semiconductor upon the doping process. This thesis contains a detailed study of the doping mechanism and the electrical properties of P3HT layers which have been p-doped by the strong molecular acceptor tetrafluorotetracyanoquinodimethane, F4TCNQ. The density of doping-induced mobile holes, their mobility, and the electrical conductivity are characterized in a broad range of acceptor concentrations. A long-standing debate on the nature of the charge transfer between P3HT and F4TCNQ is resolved by showing that almost every F4TCNQ acceptor undergoes a full-electron charge transfer with a P3HT site. However, only 5% of these charge transfer pairs can dissociate and induce a mobile hole into P3HT which contributes electrical conduction. Moreover, it is shown that the left-behind F4TCNQ ions broaden the density-of-states distribution for the doping-induced mobile holes, which is due to the longrange Coulomb attraction in the low-permittivity organic semiconductors. N2 - Organische Halbleiter kombinieren die molekulare Vielfalt und Anpassbarkeit, die mechanische Flexibilität und die preisgünstige Herstellung und Verarbeitung von Kunststoffen mit fundamentalen Halbleitereigenschaften wie Lichtabsorption und -emission und elektrischer Leitfähigkeit. Unlängst finden organische Leuchtdioden Anwendung in den Displays von TV-Geräten und Smartphones. Für die weitere Entwicklung und den Erfolg organischer Halbleiter ist das Verständnis derer physikalischer Grundlagen unabdingbar. Ein für viele Bauteile fundamentaler Prozess ist der Transport von Ladungsträgern in der organischen Schicht. Die Ladungstransporteigenschaften werden maßgeblich durch die Struktur dieser Schicht bestimmt, z.B. durch den Grad der molekularen Ordnung, die molekulare Verbindung von kristallinen Domänen und durch Defekte der molekularen Packung. Mittels optischer Spektroskopie werden in dieser Arbeit die temperatur-, molekulargewichts- und lösemittelabhängigen Struktureigenschaften poly- und oligothiophenbasierter Schichten untersucht. Dabei basiert die Analyse der Absorptionsspektren auf der Zerlegung in die spezifischen Anteile geordneten und ungeordneten Materials. Es wird gezeigt, dass sich hohe Ladungsträgerbeweglichkeiten dann erreichen lassen, wenn der Anteil der geordneten Bereiche und deren molekulare Verbindung in den Schichten möglichst hoch und die energetische Unordnung in diesen Bereichen möglichst klein ist. Der Ladungstransport in organischen Halbleitern kann außerdem gezielt beeinflusst werden, indem die Ladungsträgerdichte und die elektrische Leitfähigkeit durch molekulares Dotieren, d.h. durch das Einbringen von Elektronenakzeptoren oder -donatoren, eingestellt werden. Obwohl der Einsatz dotierter Schichten essentiell für effiziente Leuchtdioden und Solarzellen ist, ist der Mechanismus, der zur Erzeugung freier Ladungsträger im organischen Halbleiter führt, derzeit unverstanden. In dieser Arbeit wird der Ladungstransfer zwischen dem prototypischen Elektronendonator P3HT und dem Akzeptor F4TCNQ untersucht. Es wird gezeigt, dass, entgegen verbreiteter Vorstellungen, fast alle F4TCNQ-Akzeptoren einen ganzzahligen Ladungstransfer mit P3HT eingehen, aber nur 5% dieser Paare dissoziieren und einen beweglichen Ladungsträger erzeugen, der zur elektrischen Leitfähigkeit beiträgt. Weiterhin wird gezeigt, dass die zurückgelassenen F4TCNQ-Akzeptorionen Fallenzustände für die beweglichen Ladungsträger darstellen und so die Ladungsträgerbeweglichkeit in P3HT bei schwacher Dotierung absinkt. Die elektrischen Kenngrößen Ladungsträgerkonzentration, Beweglichkeit und Leitfähigkeit von F4TCNQ-dotierten P3HT-Schichten werden in dieser Arbeit erstmals in weiten Bereichen verschiedener Akzeptorkonzentrationen untersucht. KW - Polythiophen KW - organische Elektronik KW - molekulares Dotieren KW - organischer Halbleiter KW - Morphologie KW - polythiohene KW - organic electronics KW - molecular doping KW - organic semiconductor KW - morphology Y1 - 2013 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-69805 ER - TY - JOUR A1 - Schubert, Marcel A1 - Dolfen, Daniel A1 - Frisch, Johannes A1 - Roland, Steffen A1 - Steyrleuthner, Robert A1 - Stiller, Burkhard A1 - Chen, Zhihua A1 - Scherf, Ullrich A1 - Koch, Norbert A1 - Facchetti, Antonio A1 - Neher, Dieter T1 - Influence of aggregation on the performance of All-Polymer Solar Cells containing Low-Bandgap Naphthalenediimide Copolymers JF - dvanced energy materials N2 - The authors present efficient all-polymer solar cells comprising two different low-bandgap naphthalenediimide (NDI)-based copolymers as acceptors and regioregular P3HT as the donor. It is shown that these naphthalene copolymers have a strong tendency to preaggregate in specific organic solvents, and that preaggregation can be completely suppressed when using suitable solvents with large and highly polarizable aromatic cores. Organic solar cells prepared from such nonaggregated polymer solutions show dramatically increased power conversion efficiencies of up to 1.4%, which is mainly due to a large increase of the short circuit current. In addition, optimized solar cells show remarkable high fill factors of up to 70%. The analysis of the blend absorbance spectra reveals a surprising anticorrelation between the degree of polymer aggregation in the solid P3HT:NDI copolymer blends and their photovoltaic performance. Scanning near-field optical microscopy (SNOM) and atomic force microscopy (AFM) measurements reveal important information on the blend morphology. It is shown that films with high degree of aggregation and low photocurrents exhibit large-scale phase-separation into rather pure donor and acceptor domains. It is proposed that, by suppressing the aggregation of NDI copolymers at the early stage of film formation, the intermixing of the donor and acceptor component is improved, thereby allowing efficient harvesting of photogenerated excitons at the donoracceptor heterojunction. KW - aggregation KW - morphology KW - naphthalenediimide KW - organic semiconductors KW - organic photovoltaics Y1 - 2012 U6 - https://doi.org/10.1002/aenm.201100601 SN - 1614-6832 VL - 2 IS - 3 SP - 369 EP - 380 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Turner, Sarah T. A1 - Pingel, Patrick A1 - Steyrleuthner, Robert A1 - Crossland, Edward J. W. A1 - Ludwigs, Sabine A1 - Neher, Dieter T1 - Quantitative analysis of bulk heterojunction films using linear absorption spectroscopy and solar cell performance JF - Advanced functional materials N2 - A fundamental understanding of the relationship between the bulk morphology and device performance is required for the further development of bulk heterojunction organic solar cells. Here, non-optimized (chloroform cast) and nearly optimized (solvent-annealed o-dichlorobenzene cast) P3HT:PCBM blend films treated over a range of annealing temperatures are studied via optical and photovoltaic device measurements. Parameters related to the P3HT aggregate morphology in the blend are obtained through a recently established analytical model developed by F. C. Spano for the absorption of weakly interacting H-aggregates. Thermally induced changes are related to the glass transition range of the blend. In the chloroform prepared devices, the improvement in device efficiency upon annealing within the glass transition range can be attributed to the growth of P3HT aggregates, an overall increase in the percentage of chain crystallinity, and a concurrent increase in the hole mobilities. Films treated above the glass transition range show an increase in efficiency and fill factor not only associated with the change in chain crystallinity, but also with a decrease in the energetic disorder. On the other hand, the properties of the P3HT phase in the solvent-annealed o-dichlorobenzene cast blends are almost indistinguishable from those of the corresponding pristine P3HT layer and are only weakly affected by thermal annealing. Apparently, slow drying of the blend allows the P3HT chains to crystallize into large domains with low degrees of intra- and interchain disorder. This morphology appears to be most favorable for the efficient generation and extraction of charges. KW - Organic electronics KW - morphology KW - solar cells KW - mobility KW - absorption spectroscopy Y1 - 2011 U6 - https://doi.org/10.1002/adfm.201101583 SN - 1616-301X VL - 21 IS - 24 SP - 4640 EP - 4652 PB - Wiley-VCH CY - Weinheim ER - TY - THES A1 - Yin, Chunhong T1 - The interplay of nanostructure and efficiency of polymer solar cells T1 - Einfluss der Nanostruktur auf die Effizienz von Polymer-Solarzellen N2 - The aim of this thesis is to achieve a deep understanding of the working mechanism of polymer based solar cells and to improve the device performance. Two types of the polymer based solar cells are studied here: all-polymer solar cells comprising macromolecular donors and acceptors based on poly(p-phenylene vinylene) and hybrid cells comprising a PPV copolymer in combination with a novel small molecule electron acceptor. To understand the interplay between morphology and photovoltaic properties in all-polymer devices, I compared the photocurrent characteristics and excited state properties of bilayer and blend devices with different nano-morphology, which was fine tuned by using solvents with different boiling points. The main conclusion from these complementary measurements was that the performance-limiting step is the field-dependent generation of free charge carriers, while bimolecular recombination and charge extraction do not compromise device performance. These findings imply that the proper design of the donor-acceptor heterojunction is of major importance towards the goal of high photovoltaic efficiencies. Regarding polymer-small molecular hybrid solar cells I combined the hole-transporting polymer M3EH-PPV with a novel Vinazene-based electron acceptor. This molecule can be either deposited from solution or by thermal evaporation, allowing for a large variety of layer architectures to be realized. I then demonstrated that the layer architecture has a large influence on the photovoltaic properties. Solar cells with very high fill factors of up to 57 % and an open circuit voltage of 1V could be achieved by realizing a sharp and well-defined donor-acceptor heterojunction. In the past, fill factors exceeding 50 % have only been observed for polymers in combination with soluble fullerene-derivatives or nanocrystalline inorganic semiconductors as the electron-accepting component. The finding that proper processing of polymer-vinazene devices leads to similar high values is a major step towards the design of efficient polymer-based solar cells. N2 - Ziel dieser Dissertation ist es, die grundlegende Arbeitsweise von polymerbasierten Solarzellen zu verstehen und ihre Leistungsfähigkeit zu erhöhen. Zwei Arten von organischen Solarzellen werden untersucht: Solarzellen, bei denen sowohl Elektronendonator und akzeptor auf Poly(p-phenylen-vinylen) basieren sowie Zellen, bei denen ein PPV-Copolymer als Elektronendonator und organische kleine Moleküle als Elektronenakzeptor fungierten. Um die Zusammenhänge zwischen Morphologie und photovoltaischen Eigenschaften zu verstehen, untersuchte ich Photoströme sowie die Eigenschaften angeregter Zustände in Zweischicht- und Mischsolarzellen mit unterschiedlicher Nano-Morphologie, welche durch die Verwendung von Lösungsmitteln mit unterschiedlichen Siedetemperaturen modifiziert wurde. Die Hauptschlussfolgerung aus diesen Messungen ist, dass der effizienzlimitierende Faktor die feldabhängige Generation freier Ladungsträger ist, wohingegen bimolekulare Rekombination oder die Extraktion der Ladungsträger die Leistungsfähigkeit von Polymer-Polymer- Solarzellen nicht beeinträchtigen. Diese Ergebnisse legen nahe, dass die gezielte Einstellung der Donator-Akzeptor-Grenzfläche von besonderer Bedeutung zum Erreichen hoher Effizienzen ist. In Hybridsolarzellen aus Polymeren und kleinen Molekülen kombinierte ich das lochleitende konjugierte Polymer M3EH-PPV mit einem neuartigen Vinazen-Molekül als Elektronen-akzeptor. Dieses Molekül bietet die Möglichkeit, entweder aus einer Lösung heraus verarbeitet oder im Hochvakuum verdampft zu werden, wodurch eine Vielzahl an unterschiedlichen Probenstrukturen realisiert werden kann. Dadurch konnte ich zeigen, dass die Struktur der aktiven Schicht einen großen Einfluss auf die photovoltaischen Eigenschaften hat. Die Solarzellen erreichten einen Füllfaktor von bis zu 57% und eine Kurzschluss¬spannung von 1 V. In der Vergangenheit konnten bei polymerbasierten Solarzellen Füllfaktoren über 50% nur in Verbindung mit Fullerenen oder nanokristallinen anorganischen Halbleitern als Akzeptoren erreicht werden. Das Resultat, dass bei geeigneter Präparation der Polymer-Vinazen-Schicht vergleichbare Ergebnisse erzielt werden können, ist ein bedeutender Schritt hin zu effizienteren Polymersolarzellen. KW - Nanostruktur KW - Polymer-Solarzelle KW - Effizienz KW - Morphologie KW - Polymer solar cells KW - nanostructure KW - efficiency KW - morphology Y1 - 2009 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-29054 ER -