TY - JOUR A1 - Neher, Dieter A1 - Kniepert, Juliane A1 - Elimelech, Arik A1 - Koster, L. Jan Anton T1 - A New Figure of Merit for Organic Solar Cells with Transport-limited Photocurrents JF - Scientific reports N2 - Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit α to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor. KW - Electronic and spintronic devices KW - Semiconductors Y1 - 2016 U6 - https://doi.org/10.1038/srep24861 SN - 2045-2322 VL - 6 PB - Nature Publishing Group CY - London ER - TY - GEN A1 - Neher, Dieter A1 - Kniepert, Juliane A1 - Elimelech, Arik A1 - Koster, L. Jan Anton T1 - A New Figure of Merit for Organic Solar Cells with Transport-limited Photocurrents N2 - Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit α to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 225 KW - Electronic and spintronic devices KW - Semiconductors Y1 - 2016 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-91414 ER - TY - JOUR A1 - Foertig, Alexander A1 - Kniepert, Juliane A1 - Gluecker, Markus A1 - Brenner, Thomas J. K. A1 - Dyakonov, Vladimir A1 - Neher, Dieter A1 - Deibel, Carsten T1 - Nongeminate and geminate recombination in PTB7: PCBM solar cells JF - Advanced functional materials KW - organic semiconductors KW - organic solar cells KW - conjugated polymers KW - charge carrier recombination Y1 - 2014 U6 - https://doi.org/10.1002/adfm.201302134 SN - 1616-301X SN - 1616-3028 VL - 24 IS - 9 SP - 1306 EP - 1311 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Kniepert, Juliane A1 - Paulke, Andreas A1 - Perdigon-Toro, Lorena A1 - Kurpiers, Jona A1 - Zhang, Huotian A1 - Gao, Feng A1 - Yuan, Jun A1 - Zou, Yingping A1 - Le Corre, Vincent M. A1 - Koster, Lambert Jan Anton A1 - Neher, Dieter T1 - Reliability of charge carrier recombination data determined with charge extraction methods JF - Journal of applied physics N2 - Charge extraction methods are popular for measuring the charge carrier density in thin film organic solar cells and to draw conclusions about the order and coefficient of nongeminate charge recombination. However, results from such studies may be falsified by inhomogeneous steady state carrier profiles or surface recombination. Here, we present a detailed drift-diffusion study of two charge extraction methods, bias-assisted charge extraction (BACE) and time-delayed collection field (TDCF). Simulations are performed over a wide range of the relevant parameters. Our simulations reveal that both charge extraction methods provide reliable information about the recombination order and coefficient if the measurements are performed under appropriate conditions. However, results from BACE measurements may be easily affected by surface recombination, in particular for small active layer thicknesses and low illumination densities. TDCF, on the other hand, is more robust against surface recombination due to its transient nature but also because it allows for a homogeneous high carrier density to be inserted into the active layer. Therefore, TDCF is capable to provide meaningful information on the order and coefficient of recombination even if the model conditions are not exactly fulfilled. We demonstrate this for an only 100 nm thick layer of a highly efficient nonfullerene acceptor (NFA) blend, comprising the donor polymer PM6 and the NFA Y6. TDCF measurements were performed as a function of delay time for different laser fluences and bias conditions. The full set of data could be consistently fitted by a strict second order recombination process, with a bias- and fluence-independent bimolecular recombination coefficient k(2) = 1.7 x 10(-17)m(3) s(-1). BACE measurements performed on the very same layer yielded the identical result, despite the very different excitation conditions. This proves that recombination in this blend is mostly through processes in the bulk and that surface recombination is of minor importance despite the small active layer thickness. Published under license by AIP Publishing. Y1 - 2019 U6 - https://doi.org/10.1063/1.5129037 SN - 0021-8979 SN - 1089-7550 VL - 126 IS - 20 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Paulke, Andreas A1 - Stranks, Samuel D. A1 - Kniepert, Juliane A1 - Kurpiers, Jona A1 - Wolff, Christian Michael A1 - Schön, Natalie A1 - Snaith, Henry J. A1 - Brenner, Thomas J. K. A1 - Neher, Dieter T1 - Charge carrier recombination dynamics in perovskite and polymer solar cells JF - Applied physics letters N2 - Time-delayed collection field experiments are applied to planar organometal halide perovskite (CH3NH3PbI3) based solar cells to investigate charge carrier recombination in a fully working solar cell at the nanosecond to microsecond time scale. Recombination of mobile (extractable) charges is shown to follow second-order recombination dynamics for all fluences and time scales tested. Most importantly, the bimolecular recombination coefficient is found to be time-dependent, with an initial value of ca. 10(-9) cm(3)/s and a progressive reduction within the first tens of nanoseconds. Comparison to the prototypical organic bulk heterojunction device PTB7:PC71BM yields important differences with regard to the mechanism and time scale of free carrier recombination. (C) 2016 AIP Publishing LLC. Y1 - 2016 U6 - https://doi.org/10.1063/1.4944044 SN - 0003-6951 SN - 1077-3118 VL - 108 SP - 252 EP - 262 PB - American Institute of Physics CY - Melville ER - TY - JOUR A1 - Albrecht, Steve A1 - Janietz, Silvia A1 - Schindler, Wolfram A1 - Frisch, Johannes A1 - Kurpiers, Jona A1 - Kniepert, Juliane A1 - Inal, Sahika A1 - Pingel, Patrick A1 - Fostiropoulos, Konstantinos A1 - Koch, Norbert A1 - Neher, Dieter T1 - Fluorinated Copolymer PCPDTBT with enhanced open-circuit voltage and reduced recombination for highly efficient polymer solar cells JF - Journal of the American Chemical Society N2 - A novel fluorinated copolymer (F-PCPDTBT) is introduced and shown to exhibit significantly higher power conversion efficiency in bulk heterojunction solar cells with PC70BM compared to the well-known low-band-gap polymer PCPDTBT. Fluorination lowers the polymer HOMO level, resulting in high open-circuit voltages well exceeding 0.7 V. Optical spectroscopy and morphological studies with energy-resolved transmission electron microscopy reveal that the fluorinated polymer aggregates more strongly in pristine and blended layers, with a smaller amount of additives needed to achieve optimum device performance. Time-delayed collection field and charge extraction by linearly increasing voltage are used to gain insight into the effect of fluorination on the field dependence of free charge-carrier generation and recombination. F-PCPDTBT is shown to exhibit a significantly weaker field dependence of free charge-carrier generation combined with an overall larger amount of free charges, meaning that geminate recombination is greatly reduced. Additionally, a 3-fold reduction in non-geminate recombination is measured compared to optimized PCPDTBT blends. As a consequence of reduced non-geminate recombination, the performance of optimized blends of fluorinated PCPDTBT with PC70BM is largely determined by the field dependence of free-carrier generation, and this field dependence is considerably weaker compared to that of blends comprising the non-fluorinated polymer. For these optimized blends, a short-circuit current of 14 mA/cm(2), an open-circuit voltage of 0.74 V, and a fill factor of 58% are achieved, giving a highest energy conversion efficiency of 6.16%. The superior device performance and the low band-gap render this new polymer highly promising for the construction of efficient polymer-based tandem solar cells. Y1 - 2012 U6 - https://doi.org/10.1021/ja305039j SN - 0002-7863 VL - 134 IS - 36 SP - 14932 EP - 14944 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kniepert, Juliane A1 - Lange, Ilja A1 - Heidbrink, Jan A1 - Kurpiers, Jona A1 - Brenner, Thomas J. K. A1 - Koster, L. Jan Anton A1 - Neher, Dieter T1 - Effect of Solvent Additive on Generation, Recombination, and Extraction in PTB7:PCBM Solar Cells: A Conclusive Experimental and Numerical Simulation Study JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Time-delayed collection field (TDCF), bias-assisted charge extraction (BACE), and space charge-limited current (SCLC) measurements are combined with complete numerical device simulations to unveil the effect of the solvent additive 1,8-diiodooctane (DIO) on the performance of PTB7:PCBM bulk heterojunction solar cells. DIO is shown to increase the charge generation rate, reduce geminate and bimolecular recombination, and increase the electron mobility. In total, the reduction of loss currents by processing with the additive raises the power conversion efficiency of the PTB7:PCBM blend by a factor of almost three. The lower generation rates and higher geminate recombination losses in devices without DIO are consistent with a blend morphology comprising large fullerene clusters embedded within a PTB7-rich matrix, while the low electron mobility suggests that these fullerene clusters are themselves composed of smaller pure fullerene aggregates separated by disordered areas. Our device simulations show unambiguously that the effect of the additive on the shape of the currentvoltage curve (J-V) cannot be ascribed to the variation of only the mobility, the recombination, or the field dependence of generation. It is only when the changes of all three parameters are taken into account that the simulation matches the experimental J-V characteristics under all illumination conditions and for a wide range of voltages. Y1 - 2015 U6 - https://doi.org/10.1021/jp512721e SN - 1932-7447 VL - 119 IS - 15 SP - 8310 EP - 8320 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Bartesaghi, Davide A1 - Perez, Irene del Carmen A1 - Kniepert, Juliane A1 - Roland, Steffen A1 - Turbiez, Mathieu A1 - Neher, Dieter A1 - Koster, L. Jan Anton T1 - Competition between recombination and extraction of free charges determines the fill factor of organic solar cells JF - Nature Communications N2 - Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter theta, and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor: acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor: acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination. Y1 - 2015 U6 - https://doi.org/10.1038/ncomms8083 SN - 2041-1723 VL - 6 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Kniepert, Juliane A1 - Schubert, Marcel A1 - Blakesley, James C. A1 - Neher, Dieter T1 - Photogeneration and recombination in P3HT/PCBM solar cells probed by time-delayed collection field experiments JF - The journal of physical chemistry letters N2 - Time-delayed collection field (TDCF) experiments are performed on bulk heterojunction solar cells comprised of a blend of poly(3-hexylthiophene) and [6,6]-phenyl C-71 butyric acid methyl ester. TDCF is analogous to a pump-probe experiment using optical excitation and an electrical probe with a resolution of < 100 ns. The number of free charge carriers extracted after a short delay is found to be independent of the electric field during illumination. Also, experiments performed with a variable delay between the optical excitation and the electrical probe do not reveal any evidence for the generation of charge via field-assisted dissociation of bound long-lived polaron pairs. Photocurrent transients are well fitted by computational drift diffusion simulations with only direct generation of free charge carriers. With increasing delay times between pump and probe, two loss mechanisms are identified; first, charge-carriers are swept out of the device by the internal electric field, and second, bimolecular recombination of the remaining carriers takes place with a reduced recombination coefficient. Y1 - 2011 U6 - https://doi.org/10.1021/jz200155b SN - 1948-7185 VL - 2 IS - 7 SP - 700 EP - 705 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Kniepert, Juliane A1 - Lange, Ilja A1 - van der Kaap, Niels J. A1 - Koster, L. Jan Anton A1 - Neher, Dieter T1 - A conclusive view on charge generation, recombination, and extraction in As-prepared and annealed P3HT:PCBM blends: combined experimental and simulation work JF - dvanced energy materials N2 - Time-delayed collection field (TDCF) and bias-amplified charge extraction (BACE) are applied to as-prepared and annealed poly(3-hexylthiophene):[6,6]-phenyl C-71 butyric acid methyl ester (P3HT:PCBM) blends coated from chloroform. Despite large differences in fill factor, short-circuit current, and power conversion efficiency, both blends exhibit a negligible dependence of photogeneration on the electric field and strictly bimolecular recombination (BMR) with a weak dependence of the BMR coefficient on charge density. Drift-diffusion simulations are performed using the measured coefficients and mobilities, taking into account bimolecular recombination and the possible effects of surface recombination. The excellent agreement between the simulation and the experimental data for an intensity range covering two orders of magnitude indicates that a field-independent generation rate and a density-independent recombination coefficient describe the current-voltage characteristics of the annealed P3HT: PCBM devices, while the performance of the as-prepared blend is shown to be limited by space charge effects due to a low hole mobility. Finally, even though the bimolecular recombination coefficient is small, surface recombination is found to be a negligible loss mechanism in these solar cells. Y1 - 2014 U6 - https://doi.org/10.1002/aenm.201301401 SN - 1614-6832 SN - 1614-6840 VL - 4 IS - 7 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Neher, Dieter A1 - Kniepert, Juliane A1 - Elimelech, Arik A1 - Koster, L. Jan Anton T1 - A New Figure of Merit for Organic Solar Cells with Transport-limited Photocurrents JF - Scientific reports N2 - Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit a to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor. Y1 - 2016 U6 - https://doi.org/10.1038/srep24861 SN - 2045-2322 VL - 6 SP - E2348 EP - E2349 PB - Nature Publ. Group CY - London ER - TY - THES A1 - Kniepert, Juliane T1 - Correlation between dynamic parameters and device performance of organic solar cells T1 - Zusammenhang zwischen den dynamischen Größen und der Effizienz Organischer Solarzellen N2 - Organic bulk heterojunction (BHJ) solar cells based on polymer:fullerene blends are a promising alternative for a low-cost solar energy conversion. Despite significant improvements of the power conversion efficiency in recent years, the fundamental working principles of these devices are yet not fully understood. In general, the current output of organic solar cells is determined by the generation of free charge carriers upon light absorption and their transport to the electrodes in competition to the loss of charge carriers due to recombination. The object of this thesis is to provide a comprehensive understanding of the dynamic processes and physical parameters determining the performance. A new approach for analyzing the characteristic current-voltage output was developed comprising the experimental determination of the efficiencies of charge carrier generation, recombination and transport, combined with numerical device simulations. Central issues at the beginning of this work were the influence of an electric field on the free carrier generation process and the contribution of generation, recombination and transport to the current-voltage characteristics. An elegant way to directly measure the field dependence of the free carrier generation is the Time Delayed Collection Field (TDCF) method. In TDCF charge carriers are generated by a short laser pulse and subsequently extracted by a defined rectangular voltage pulse. A new setup was established with an improved time resolution compared to former reports in literature. It was found that charge generation is in general independent of the electric field, in contrast to the current view in literature and opposed to the expectations of the Braun-Onsager model that was commonly used to describe the charge generation process. Even in cases where the charge generation was found to be field-dependend, numerical modelling showed that this field-dependence is in general not capable to account for the voltage dependence of the photocurrent. This highlights the importance of efficient charge extraction in competition to non-geminate recombination, which is the second objective of the thesis. Therefore, two different techniques were combined to characterize the dynamics and efficiency of non-geminate recombination under device-relevant conditions. One new approach is to perform TDCF measurements with increasing delay between generation and extraction of charges. Thus, TDCF was used for the first time to measure charge carrier generation, recombination and transport with the same experimental setup. This excludes experimental errors due to different measurement and preparation conditions and demonstrates the strength of this technique. An analytic model for the description of TDCF transients was developed and revealed the experimental conditions for which reliable results can be obtained. In particular, it turned out that the $RC$ time of the setup which is mainly given by the sample geometry has a significant influence on the shape of the transients which has to be considered for correct data analysis. Secondly, a complementary method was applied to characterize charge carrier recombination under steady state bias and illumination, i.e. under realistic operating conditions. This approach relies on the precise determination of the steady state carrier densities established in the active layer. It turned out that current techniques were not sufficient to measure carrier densities with the necessary accuracy. Therefore, a new technique {Bias Assisted Charge Extraction} (BACE) was developed. Here, the charge carriers photogenerated under steady state illumination are extracted by applying a high reverse bias. The accelerated extraction compared to conventional charge extraction minimizes losses through non-geminate recombination and trapping during extraction. By performing numerical device simulations under steady state, conditions were established under which quantitative information on the dynamics can be retrieved from BACE measurements. The applied experimental techniques allowed to sensitively analyse and quantify geminate and non-geminate recombination losses along with charge transport in organic solar cells. A full analysis was exemplarily demonstrated for two prominent polymer-fullerene blends. The model system P3HT:PCBM spincast from chloroform (as prepared) exhibits poor power conversion efficiencies (PCE) on the order of 0.5%, mainly caused by low fill factors (FF) and currents. It could be shown that the performance of these devices is limited by the hole transport and large bimolecular recombination (BMR) losses, while geminate recombination losses are insignificant. The low polymer crystallinity and poor interconnection between the polymer and fullerene domains leads to a hole mobility of the order of 10^-7 cm^2/Vs which is several orders of magnitude lower than the electron mobility in these devices. The concomitant build up of space charge hinders extraction of both electrons and holes and promotes bimolecular recombination losses. Thermal annealing of P3HT:PCBM blends directly after spin coating improves crystallinity and interconnection of the polymer and the fullerene phase and results in comparatively high electron and hole mobilities in the order of 10^-3 cm^2/Vs and 10^-4 cm^2/Vs, respectively. In addition, a coarsening of the domain sizes leads to a reduction of the BMR by one order of magnitude. High charge carrier mobilities and low recombination losses result in comparatively high FF (>65%) and short circuit current (J_SC ≈ 10 mA/cm^2). The overall device performance (PCE ≈ 4%) is only limited by a rather low spectral overlap of absorption and solar emission and a small V_OC, given by the energetics of the P3HT. From this point of view the combination of the low bandgap polymer PTB7 with PCBM is a promising approach. In BHJ solar cells, this polymer leads to a higher V_OC due to optimized energetics with PCBM. However, the J_SC in these (unoptimized) devices is similar to the J_SC in the optimized blend with P3HT and the FF is rather low (≈ 50%). It turned out that the unoptimized PTB7:PCBM blends suffer from high BMR, a low electron mobility of the order of 10^-5 cm^2/Vs and geminate recombination losses due to field dependent charge carrier generation. The use of the solvent additive DIO optimizes the blend morphology, mainly by suppressing the formation of very large fullerene domains and by forming a more uniform structure of well interconnected donor and acceptor domains of the order of a few nanometers. Our analysis shows that this results in an increase of the electron mobility by about one order of magnitude (3 x 10^-4 cm^2/Vs), while BMR and geminate recombination losses are significantly reduced. In total these effects improve the J_SC (≈ 17 mA/cm^2) and the FF (> 70%). In 2012 this polymer/fullerene combination resulted in a record PCE for a single junction OSC of 9.2%. Remarkably, the numerical device simulations revealed that the specific shape of the J-V characteristics depends very sensitively to the variation of not only one, but all dynamic parameters. On the one hand this proves that the experimentally determined parameters, if leading to a good match between simulated and measured J-V curves, are realistic and reliable. On the other hand it also emphasizes the importance to consider all involved dynamic quantities, namely charge carrier generation, geminate and non-geminate recombination as well as electron and hole mobilities. The measurement or investigation of only a subset of these parameters as frequently found in literature will lead to an incomplete picture and possibly to misleading conclusions. Importantly, the comparison of the numerical device simulation employing the measured parameters and the experimental $J-V$ characteristics allows to identify loss channels and limitations of OSC. For example, it turned out that inefficient extraction of charge carriers is a criticical limitation factor that is often disobeyed. However, efficient and fast transport of charges becomes more and more important with the development of new low bandgap materials with very high internal quantum efficiencies. Likewise, due to moderate charge carrier mobilities, the active layer thicknesses of current high-performance devices are usually limited to around 100 nm. However, larger layer thicknesses would be more favourable with respect to higher current output and robustness of production. Newly designed donor materials should therefore at best show a high tendency to form crystalline structures, as observed in P3HT, combined with the optimized energetics and quantum efficiency of, for example, PTB7. N2 - Organische Solarzellen aus Polymer-Fulleren Mischschichten sind eine vielversprechende Alternative für eine kostengünstige Quelle erneuerbarer Energien. Jedoch sind trotz intensiver Forschung und bedeutenden Verbesserungen der Effizienzen während der letzten Jahre, die fundamentalen Prozesse in diesen Solarzellen noch immer nicht vollständig verstanden. Im Allgemeinen wird der Photostrom in organischen Solarzellen durch die Generation freier Ladungsträger nach Absorption von Licht und dem anschliessenden Transport dieser Ladungsträger zu den Elektroden bestimmt, wobei ein Teil durch Rekombination verloren geht. Das Ziel dieser Dissertation ist es, zu einem umfassenden Verständnis aller dynamischen Prozesse und relevanten physikalischen Parameter und deren Zusammenhang mit der Solarzelleneffizienz beizutragen. Dabei wurde eine neue Herangehensweise zur Analyse der Strom-Spannungskennlinien entwickelt, die auf der experimentellen Bestimmung von Ladungsträgergeneration, Rekombination und Transport im Vergleich mit numerischen Simulationen beruht. Die zentralen Fragestellungen zu Beginn der Arbeit waren, in welchem Masse die Ladungsträgergeneration von der Stärke des elektrischen Feldes abhängt und in wie weit die einzelnen Prozesse Generation, Rekombination und Transport zum charakteristischen Verlauf der Strom-Spannungskennlinie beitragen. Eine elegante Methode um direkt die Feldabhängigkeit der Ladungsträgergeneration zu bestimmen, ist die Time Delayed Collection Field (TDCF) Methode. Dabei werden in der Solarzelle Ladungsträger mit einem kurzen Laserpuls erzeugt und anschliessend mit einem wohldefinierten rechteckigen Spannungspuls extrahiert. Im Rahmen dieser Arbeit wurde ein neuer Versuchsaufbau mit stark verbesserter Zeitauflösung im Vergleich zu vorangegangenen Arbeiten aufgebaut. Es hat sich gezeigt, dass die Generation im Allgemeinen nicht vom elektrischen Feld abhängt. Dies steht im Widerspruch zu dem in der Literatur häufig verwendeten Braun-Onsager Modell zur Beschreibung der Ladungsgeneration. Selbst in Fällen, in denen eine feldabhängige Generation gemessen wurde, reichte diese im Allgemeinen nicht aus, um die Spannungsabhängigkeit des Photostroms in diesen Zellen zu erklären. Dies führt zu der zunehmenden Bedeutung einer effizienten Ladungsextraktion in Konkurrenz zur nicht-geminalen Rekombination, welche die zweite wichtige Fragestellung in dieser Arbeit war. Dazu wurden zwei neue Herangehensweisen zur Messung der Rekombinationsdynamik unter Solarzellen-relevanten Messbedingungen erarbeitet. Zum Einen wurde zum ersten Mal TDCF zur Messung von Rekombination und Transport verwendet. Der Vorteil ist, dass die Messung aller drei relevanten Prozesse in einem Versuchsaufbau zu einer höheren Genauigkeit führt, da experimentelle Fehler durch unterschiedliche Probenpräparation und Messbedingungen ausgeschlossen werden können. Es wurde ein analytisches Modell zur Beschreibung der TDCF Transienten entwickelt, welches direkt Rückschlüsse auf die notwendigen Messbedingungen erlaubt, unter denen zuverlässige Ergebnisse erzielt werden können. Insbesondere hat sich dabei gezeigt, dass die RC-Zeit des Aufbaus, die hauptsächlich durch die Probengeometrie bestimmt wird, einen wesentlichen Einfluss auf die Transienten hat, welcher in der Datenauswertung nicht vernachlässigt werden darf. Zum Anderen wurde eine komplementäre Methode zur Messung der Rekombination im Gleichgewicht benutzt, die auf der genauen Bestimmung der statischen Ladungsträgerdichte unter Beleuchtung basiert. Es zeigte sich, dass die in der Literatur etablierten Methoden zur Ladungsträgerbestimmung nicht ausreichend genau waren. Daher wurde eine neue, sensitive Technik entwickelt, die Bias Assisted Charge Extraction (BACE) Methode. Dabei werden die unter kontinuierlicher Beleuchtung generierten Ladungsträger mit einem hohen angelegten elektrischen Feld extrahiert. Dies führt zu einer beschleunigten Extraktion im Vergleich zur konventionellen Charge Extraction Methode, welche die Verluste durch Rekombination und Trapping deutlich reduziert. Mit Hilfe von numerischen Simulationen wurden Bedingungen festgelegt, unter denen zuverlässige Messungen mit BACE möglich sind. Mit den vorgestellten Methoden können alle relevanten Parameter für Generation, Rekombination und Transport experimentell sehr genau bestimmt und analysiert werden. Dies wurde exemplarisch für zwei in der Literatur bedeutende Materialsysteme durchgeführt. Das Modellsystem P3HT:PCBM, hergestellt aus dem Lösungsmittel Chloroform, weist direkt nach der Präparation nur sehr niedrige Effizienzen im Bereich von 0.5% auf, die vor allem durch niedrige Ströme und Füllfaktoren (FF) gekennzeichnet sind. Es konnte gezeigt werden, dass die Effizienz dieser Zellen durch den sehr langsamen Lochtransport und die starke bimolekulare Rekombination begrenzt wird, während Verluste durch geminale Rekombination eher unbedeutend sind. Eine geringe Kristallinität des Polymers und schlechte Verbindungen zwischen den Polymerdomänen führt zu einer Lochmobilität von nur 10^7 cm^2/Vs. Diese ist mehrere Grössenordnungen kleiner als die Elektronenmobilität in diesen Zellen, was den Aufbau von Raumladungen zur Folge hat und damit die Extraktion von beiden Ladungsträgern behindert und bimolekulare Rekombination begünstigt. Die thermische Behandlung der P3HT:PCBM Proben direkt nach dem Spin Coating verbessert sowohl die Kristallinität als auch die Vernetzung der Polymer- und Fullerenphasen. Dies führt zu vergleichsweise hohen Mobilitäten für Elektronen (10^3 cm^2/Vs) und Löcher (10^4 cm^2/Vs). Zusätzlich reduziert eine Vergrösserung der Domänenstruktur die bimolekulare Rekombination um eine Grössenordnung. Die hohen Mobilitäten und niedrigen Rekombinationverluste resultieren in vergleichsweise hohen FF (> 65%) und Strömen (J_SC ≈ 10 mA/cm^2). Die Effizienz (≈ 4%) wird dabei nur durch den eher geringen spektralen Überlapp zwischen Absorptions- und Sonnenemissionsspektrum begrenzt und einer geringen Leerlaufspannung (V_OC), verursacht durch die ungünstige Energetik des P3HT. Aus dieser Perspektive ist die Kombination des Low-Bandgap Polymers PTB7 mit dem Fullerenderivat PCBM ein vielversprechender Ansatz. Aufgrund der angepassten Energetik führt diese Kombination in Mischschichtsolarzellen zu einer höheren V_OC. Jedoch ist der Kurzschlussstrom (J_SC) in den unoptimierten Zellen gegenüber dem der optimierten P3HT:PCBM Zellen nicht erhöht und die FF sind niedrig (≈ 50%). Die Untersuchungen ergaben, dass die Dynamik in den unoptimierten PTB7:PCBM Zellen durch hohe bimolekulare Rekombination (BMR), eine niedrige Elektronenmobilität im Bereich von 10^5 cm^2/Vs und nicht-geminalen Rekombinationsverslusten aufgrund einer feldabhängigen Generation geprägt ist. Die Zugabe des Lösungsmitteladditivs DIO bei der Probenpräparation optimiert die Morphologie in der Schicht. Dabei wird hauptsächlich die Formation von sehr grossen Fullerendomänen unterdrückt und eine gleichmässige Struktur von gut vernetzten, nanometergrossen Donor- und Akzeptordomänen ausgebildet. Unsere Analyse zeigt, dass dadurch die Elektronenmobilität um ca eine Grössenordnung erhöht wird (auf 3 x 10^4 cm^2/Vs), während BMR und geminale Rekombination deutlich unterdrückt werden. Zusammen genommen verbessern diese Effekte sowohl den J_SC (≈ 17 mA/cm^2) als auch den FF (> 70%). Im Jahr 2012 führten die optimierten PTB7:PCBM Solarzellen damit zu einer Rekordeffizienz für organische Solarzellen von 9.2%. Von grösserer Bedeutung ist jedoch, dass der Vergleich zwischen den gemessenen und simulierten Strom-Spannungskennlinien, mit experimentell bestimmten Eingangsparametern, Rückschlüsse auf die entsprechenden Verlustkanäle in den jeweiligen Solarzellen erlaubt. Hierbei zeigte sich, dass die effiziente Extraktion von Ladungsträgern ein kritischer Faktor ist, der in der Literatur oft unterschätzt wird. Der effiziente und schnelle Transport von Ladungen wird aber gerade im Hinblick auf neue Low-Bandgap Materialien mit sehr hohen internen Quanteneffizienzen immer wichtiger. Moderate Mobilitäten limitieren die möglichen Schichtdicken auf ca 100 nm. Grössere Schichtdicken wären jedoch vorteilhafter im Hinblick auf höhere Ausgangsströme und der Robustheit des Produktionsprozesses. Neu entwickelte Donormaterialien sollten daher sowohl möglichst kristalline Strukturen ausbilden mit einhergehenden hohen Mobilitäten, wie beim P3HT, als auch optimierte Energieniveaus und Quanteneffizienzen aufweisen, wie beispielsweise PTB7. KW - organic solar cells KW - optoelectronic measurements KW - transient methods KW - numeric device simulations KW - organische Solarzellen KW - optoelektronische Messungen KW - transiente Messmethoden KW - numerische Bauteilsimulationen Y1 - 2015 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-90087 ER - TY - JOUR A1 - Albrecht, Steve A1 - Schindler, Wolfram A1 - Kurpiers, Jona A1 - Kniepert, Juliane A1 - Blakesley, James C. A1 - Dumsch, Ines A1 - Allard, Sybille A1 - Fostiropoulos, Konstantinos A1 - Scherf, Ullrich A1 - Neher, Dieter T1 - On the field dependence of free charge carrier generation and recombination in blends of PCPDTBT/PC70BM influence of solvent additives JF - The journal of physical chemistry letters N2 - We have applied time-delayed collection field (TDCF) and charge extraction by linearly increasing voltage (CELIV) to investigate the photogeneration, transport, and recombination of charge carriers in blends composed of PCPDTBT/PC70BM processed with and without the solvent additive diiodooctane. The results suggest that the solvent additive has severe impacts on the elementary processes involved in the photon to collected electron conversion in these blends. First, a pronounced field dependence of the free carrier generation is found for both blends, where the field dependence is stronger without the additive. Second, the fate of charge carriers in both blends can be described with a rather high bimolecular recombination coefficients, which increase with decreasing internal field. Third, the mobility is three to four times higher with the additive. Both blends show a negative field dependence of mobility, which we suggest to cause bias-dependent recombination coefficients. Y1 - 2012 U6 - https://doi.org/10.1021/jz3000849 SN - 1948-7185 VL - 3 IS - 5 SP - 640 EP - 645 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lange, Ilja A1 - Kniepert, Juliane A1 - Pingel, Patrick A1 - Dumsch, Ines A1 - Allard, Sybille A1 - Janietz, Silvia A1 - Scherf, Ullrich A1 - Neher, Dieter T1 - Correlation between the open circuit voltage and the energetics of organic bulk heterojunction solar cells JF - The journal of physical chemistry letters N2 - A detailed investigation of the open circuit voltage (V-OC) of organic bulk heterojunction solar cells comprising three different donor polymers and two different fullerene-based acceptors is presented. Bias amplified charge extraction (BACE) is combined with Kelvin Probe measurements to derive information on the relevant energetics in the blend. On the example of P3HT:PC70BM the influence of composition and preparation conditions on the relevant transport levels will be shown. Moderate upward shifts of the P3HT HOMO depending on crystallinity are observed, but contrarily to common believe, the dependence of V-OC on blend composition and thermal history is found to be largely determined by the change in the PCBM LUMO energy. Following this approach, we quantified the energetic contribution to the V-OC in blends with fluorinated polymers or higher adduct fullerenes. Y1 - 2013 U6 - https://doi.org/10.1021/jz401971e SN - 1948-7185 VL - 4 IS - 22 SP - 3865 EP - 3871 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Roland, Steffen A1 - Kniepert, Juliane A1 - Love, John A. A1 - Negi, Vikas A1 - Liu, Feilong A1 - Bobbert, Peter A1 - Melianas, Armantas A1 - Kemerink, Martijn A1 - Hofacker, Andreas A1 - Neher, Dieter T1 - Equilibrated Charge Carrier Populations Govern Steady-State Nongeminate Recombination in Disordered Organic Solar Cells JF - The journal of physical chemistry letters N2 - We employed bias-assisted charge extraction techniques to investigate the transient and steady-state recombination of photogenerated charge carriers in complete devices of a disordered polymer-fullerene blend. Charge recombination is shown to be dispersive, with a significant slowdown of the recombination rate over time, consistent with the results from kinetic Monte Carlo simulations. Surprisingly, our experiments reveal little to no contributions from early time recombination of nonequilibrated charge carriers to the steady-state recombination properties. We conclude that energetic relaxation of photogenerated carriers outpaces any significant nongeminate recombination under application-relevant illumination conditions. With equilibrated charges dominating the steady-state recombination, quasi-equilibrium concepts appear suited for describing the open-circuit voltage of organic solar cells despite pronounced energetic disorder. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpclett.9b00516 SN - 1948-7185 VL - 10 IS - 6 SP - 1374 EP - 1381 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Lange, Ilja A1 - Reiter, Sina A1 - Kniepert, Juliane A1 - Piersimoni, Fortunato A1 - Paetzel, Michael A1 - Hildebrandt, Jana A1 - Brenner, Thomas J. K. A1 - Hecht, Stefan A1 - Neher, Dieter T1 - Zinc oxide modified with benzylphosphonic acids as transparent electrodes in regular and inverted organic solar cell structures JF - Applied physics letters N2 - An approach is presented to modify the work function of solution-processed sol-gel derived zinc oxide (ZnO) over an exceptionally wide range of more than 2.3 eV. This approach relies on the formation of dense and homogeneous self-assembled monolayers based on phosphonic acids with different dipole moments. This allows us to apply ZnO as charge selective bottom electrodes in either regular or inverted solar cell structures, using poly(3-hexylthiophene): phenyl-C71-butyric acid methyl ester as the active layer. These devices compete with or even surpass the performance of the reference on indium tin oxide/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Our findings highlight the potential of properly modified ZnO as electron or hole extracting electrodes in hybrid optoelectronic devices. (C) 2015 AIP Publishing LLC. Y1 - 2015 U6 - https://doi.org/10.1063/1.4916182 SN - 0003-6951 SN - 1077-3118 VL - 106 IS - 11 PB - American Institute of Physics CY - Melville ER -