@article{LigorioNardiSteyrleuthneretal.2016, author = {Ligorio, G. and Nardi, M. V. and Steyrleuthner, Robert and Ihiawakrim, D. and Crespo-Monteiro, N. and Brinkmann, Martin and Neher, Dieter and Koch, N.}, title = {Metal nanoparticle mediated space charge and its optical control in an organic hole-only device}, series = {Applied physics letters}, volume = {108}, journal = {Applied physics letters}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.4945710}, pages = {5}, year = {2016}, abstract = {We reveal the role of localized space charges in hole-only devices based on an organic semiconductor with embedded metal nanoparticles (MNPs). MNPs act as deep traps for holes and reduce the current density compared to a device without MNPs by a factor of 10(4) due to the build-up of localized space charge. Dynamic MNPs charged neutrality can be realized during operation by electron transfer from excitons created in the organic matrix, enabling light sensing independent of device bias. In contrast to the previous speculations, electrical bistability in such devices was not observed. (C) 2016 AIP Publishing LLC.}, language = {en} } @article{ZersonNeumannSteyrleuthneretal.2016, author = {Zerson, Mario and Neumann, Martin and Steyrleuthner, Robert and Neher, Dieter and Magerle, Robert}, title = {Surface Structure of Semicrystalline Naphthalene Diimide-Bithiophene Copolymer Films Studied with Atomic Force Microscopy}, series = {Macromolecules : a publication of the American Chemical Society}, volume = {49}, journal = {Macromolecules : a publication of the American Chemical Society}, publisher = {American Chemical Society}, address = {Washington}, issn = {0024-9297}, doi = {10.1021/acs.macromol.6b00988}, pages = {6549 -- 6557}, year = {2016}, language = {en} } @article{ColladoFregosoHoodShoaeeetal.2017, author = {Collado-Fregoso, Elisa and Hood, Samantha N. and Shoaee, Safa and Schr{\"o}der, Bob C. and McCulloch, Iain and Kassal, Ivan and Neher, Dieter and Durrant, James R.}, title = {Intercalated vs Nonintercalated Morphologies in Donor-Acceptor Bulk Heterojunction Solar Cells: PBTTT:Fullerene Charge Generation and Recombination Revisited}, series = {The journal of physical chemistry letters}, volume = {8}, journal = {The journal of physical chemistry letters}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.7b01571}, pages = {4061 -- 4068}, year = {2017}, abstract = {In this Letter, we study the role of the donor:acceptor interface nanostructure upon charge separation and recombination in organic photovoltaic devices and blend films, using mixtures of PBTTT and two different fullerene derivatives (PC70BM and ICTA) as models for intercalated and nonintercalated morphologies, respectively. Thermodynamic simulations show that while the completely intercalated system exhibits a large free-energy barrier for charge separation, this barrier is significantly lower in the nonintercalated system and almost vanishes when energetic disorder is included in the model. Despite these differences, both femtosecond-resolved transient absorption spectroscopy (TAS) and time-delayed collection field (TDCF) exhibit extensive first-order losses in both systems, suggesting that geminate pairs are the primary product of photoexcitation. In contrast, the system that comprises a combination of fully intercalated polymer:fullerene areas and fullerene-aggregated domains (1:4 PBTTT:PC70BM) is the only one that shows slow, second-order recombination of free charges, resulting in devices with an overall higher short-circuit current and fill factor. This study therefore provides a novel consideration of the role of the interfacial nanostructure and the nature of bound charges and their impact upon charge generation and recombination.}, language = {en} } @article{NikolisBenduhnHolzmuelleretal.2017, author = {Nikolis, Vasileios C. and Benduhn, Johannes and Holzmueller, Felix and Piersimoni, Fortunato and Lau, Matthias and Zeika, Olaf and Neher, Dieter and Koerner, Christian and Spoltore, Donato and Vandewal, Koen}, title = {Reducing Voltage Losses in Cascade Organic Solar Cells while Maintaining High External Quantum Efficiencies}, series = {dvanced energy materials}, volume = {7}, journal = {dvanced energy materials}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.201700855}, pages = {122 -- 136}, year = {2017}, abstract = {High photon energy losses limit the open-circuit voltage (V-OC) and power conversion efficiency of organic solar cells (OSCs). In this work, an optimization route is presented which increases the V-OC by reducing the interfacial area between donor (D) and acceptor (A). This optimization route concerns a cascade device architecture in which the introduction of discontinuous interlayers between alpha-sexithiophene (alpha-6T) (D) and chloroboron subnaphthalocyanine (SubNc) (A) increases the V-OC of an alpha-6T/SubNc/SubPc fullerene-free cascade OSC from 0.98 V to 1.16 V. This increase of 0.18 V is attributed solely to the suppression of nonradiative recombination at the D-A interface. By accurately measuring the optical gap (E-opt) and the energy of the charge-transfer state (E-CT) of the studied OSC, a detailed analysis of the overall voltage losses is performed. E-opt - qV(OC) losses of 0.58 eV, which are among the lowest observed for OSCs, are obtained. Most importantly, for the V-OC-optimized devices, the low-energy (700 nm) external quantum efficiency (EQE) peak remains high at 79\%, despite a minimal driving force for charge separation of less than 10 meV. This work shows that low-voltage losses can be combined with a high EQE in organic photovoltaic devices.}, language = {en} } @article{HofackerNeher2017, author = {Hofacker, Andreas and Neher, Dieter}, title = {Dispersive and steady-state recombination in organic disordered semiconductors}, series = {Physical review : B, Condensed matter and materials physics}, volume = {96}, journal = {Physical review : B, Condensed matter and materials physics}, publisher = {American Physical Society}, address = {College Park}, issn = {2469-9950}, doi = {10.1103/PhysRevB.96.245204}, pages = {5640 -- 5649}, year = {2017}, abstract = {Charge carrier recombination in organic disordered semiconductors is strongly influenced by the thermalization of charge carriers in the density of states (DOS). Measurements of recombination dynamics, conducted under transient or steady-state conditions, can easily be misinterpreted when a detailed understanding of the interplay of thermalization and recombination is missing. To enable adequate measurement analysis, we solve the multiple-trapping problem for recombining charge carriers and analyze it in the transient and steady excitation paradigm for different DOS distributions. We show that recombination rates measured after pulsed excitation are inherently time dependent since recombination gradually slows down as carriers relax in the DOS. When measuring the recombination order after pulsed excitation, this leads to an apparent high-order recombination at short times. As times goes on, the recombination order approaches an asymptotic value. For the Gaussian and the exponential DOS distributions, this asymptotic value equals the recombination order of the equilibrated system under steady excitation. For a more general DOS distribution, the recombination order can also depend on the carrier density, under both transient and steady-state conditions. We conclude that transient experiments can provide rich information about recombination in and out of equilibrium and the underlying DOS occupation provided that consistent modeling of the system is performed.}, language = {en} } @article{MechauSaphiannikovaNeher2006, author = {Mechau, Norman and Saphiannikova, Marina and Neher, Dieter}, title = {Molecular tracer diffusion in thin azobenzene polymer layers}, series = {Applied physics letters}, volume = {89}, journal = {Applied physics letters}, number = {25}, publisher = {Elsevier}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.2405853}, pages = {3}, year = {2006}, abstract = {Translational diffusion of fluorescent tracer molecules in azobenzene polymer layers is studied at different temperatures and under illumination using the method of fluorescence recovery after photobleaching. Diffusion is clearly observed in the dark above the glass transition temperature, while homogeneous illumination at 488 nm and 100 mW/cm(2) does not cause any detectable diffusion of the dye molecules within azobenzene layers. This implies that the viscosity of azobenzene layers remains nearly unchanged under illumination with visible light in the absence of internal or external forces. (c) 2006 American Institute of Physics.}, language = {en} } @article{AlqahtaniBabicsGorenflotetal.2018, author = {Alqahtani, Obaid and Babics, Maxime and Gorenflot, Julien and Savikhin, Victoria and Ferron, Thomas and Balawi, Ahmed H. and Paulke, Andreas and Kan, Zhipeng and Pope, Michael and Clulow, Andrew J. and Wolf, Jannic and Burn, Paul L. and Gentle, Ian R. and Neher, Dieter and Toney, Michael F. and Laquai, Frederic and Beaujuge, Pierre M. and Collins, Brian A.}, title = {Mixed Domains Enhance Charge Generation and Extraction in Bulk-Heterojunction Solar Cells with Small-Molecule Donors}, series = {Advanced energy materials}, volume = {8}, journal = {Advanced energy materials}, number = {19}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.201702941}, pages = {16}, year = {2018}, abstract = {The interplay between nanomorphology and efficiency of polymer-fullerene bulk-heterojunction (BHJ) solar cells has been the subject of intense research, but the generality of these concepts for small-molecule (SM) BHJs remains unclear. Here, the relation between performance; charge generation, recombination, and extraction dynamics; and nanomorphology achievable with two SM donors benzo[1,2-b:4,5-b]dithiophene-pyrido[3,4-b]-pyrazine BDT(PPTh2)(2), namely SM1 and SM2, differing by their side-chains, are examined as a function of solution additive composition. The results show that the additive 1,8-diiodooctane acts as a plasticizer in the blends, increases domain size, and promotes ordering/crystallinity. Surprisingly, the system with high domain purity (SM1) exhibits both poor exciton harvesting and severe charge trapping, alleviated only slightly with increased crystallinity. In contrast, the system consisting of mixed domains and lower crystallinity (SM2) shows both excellent exciton harvesting and low charge recombination losses. Importantly, the onset of large, pure crystallites in the latter (SM2) system reduces efficiency, pointing to possible differences in the ideal morphologies for SM-based BHJ solar cells compared with polymer-fullerene devices. In polymer-based systems, tie chains between pure polymer crystals establish a continuous charge transport network, whereas SM-based active layers may in some cases require mixed domains that enable both aggregation and charge percolation to the electrodes.}, language = {en} } @article{LiBenduhnLietal.2018, author = {Li, Tian-yi and Benduhn, Johannes and Li, Yue and Jaiser, Frank and Spoltore, Donato and Zeika, Olaf and Ma, Zaifei and Neher, Dieter and Vandewal, Koen and Leo, Karl}, title = {Boron dipyrromethene (BODIPY) with meso-perfluorinated alkyl substituents as near infrared donors in organic solar cells}, series = {Journal of materials chemistry : A, Materials for energy and sustainability}, volume = {6}, journal = {Journal of materials chemistry : A, Materials for energy and sustainability}, number = {38}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-7488}, doi = {10.1039/c8ta06261g}, pages = {18583 -- 18591}, year = {2018}, abstract = {Three furan-fused BODIPYs were synthesized with perfluorinated methyl, ethyl and n-propyl groups on the meso-carbon. They were obtained with high yields by reacting the furan-fused 2-carboxylpyrrole in corresponding perfluorinated acid and anhydride. With the increase in perfluorinated alkyl chain length, the molecular packing in the single crystal is influenced, showing increasing stacking distance and decreasing slope angle. All the BODIPYs were characterized as intense absorbers in near infrared region in solid state, peaking at similar to 800 nm with absorption coefficient of over 280 000 cm(-1). Facilitated by high thermal stability, the furan-fused BODIPYs were employed in vacuum-deposited organic solar cells as electron donors. All devices exhibit PCE over 6.0\% with the EQE maximum reaching 70\% at similar to 790 nm. The chemical modification of the BODIPY donors have certain influence on the active layer morphology, and the highest PCE of 6.4\% was obtained with a notably high jsc of 13.6 mA cm(-2). Sensitive EQE and electroluminance studies indicated that the energy losses generated by the formation of a charge transfer state and the radiative recombination at the donor-acceptor interface were comparable in the range of 0.14-0.19 V, while non-radiative recombination energy loss of 0.38 V was the main energy loss route resulting in the moderate V-oc of 0.76 V.}, language = {en} } @article{SalertKruegerBagnichetal.2013, author = {Salert, Beatrice Ch. D. and Krueger, Hartmut and Bagnich, Sergey A. and Unger, Thomas and Jaiser, Frank and Al-Sa'di, Mahmoud and Neher, Dieter and Hayer, Anna and Eberle, Thomas}, title = {New polymer matrix system for phosphorescent organic light-emitting diodes and the role of the small molecular co-host}, series = {Journal of polymer science : A, Polymer chemistry}, volume = {51}, journal = {Journal of polymer science : A, Polymer chemistry}, number = {3}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0887-624X}, doi = {10.1002/pola.26409}, pages = {601 -- 613}, year = {2013}, abstract = {A new matrix system for phosphorescent organic light-emitting diodes (OLEDs) based on an electron transporting component attached to an inert polymer backbone, an electronically neutral co-host, and a phosphorescent dye that serves as both emitter and hole conductor are presented. The inert co-host is used either as small molecules or covalently connected to the same chain as the electron-transporting host. The use of a small molecular inert co-host in the active layer is shown to be highly advantageous in comparison to a purely polymeric matrix bearing the same functionalities. Analysis of the dye phosphorescence decay in pure polymer, small molecular co-host film, and their blend lets to conclude that dye molecules distribute mostly in the small molecular co-host phase, where the co-host prevents agglomeration and self-quenching of the phosphorescence as well as energy transfer to the electron transporting units. In addition, the co-host accumulates at the anode interface where it acts as electron blocking layer and improves hole injection. This favorable phase separation between polymeric and small molecular components results in devices with efficiencies of about 47 cd/A at a luminance of 1000 cd/m(2). Investigation of OLED degradation demonstrates the presence of two time regimes: one fast component that leads to a strong decrease at short times followed by a slower decrease at longer times. Unlike the long time degradation, the efficiency loss that occurs at short times is reversible and can be recovered by annealing of the device at 180 degrees C. We also show that the long-time degradation must be related to a change of the optical and electrical bulk properties.}, language = {en} } @article{ZenPflaumHirschmannetal.2004, author = {Zen, Achmad and Pflaum, J. and Hirschmann, S. and Zhuang, W. and Jaiser, Frank and Asawapirom, Udom and Rabe, J. P. and Scherf, Ullrich and Neher, Dieter}, title = {Effect of molecular weight and annealing of poly (3-hexylthiophene)s on the performance of organic field-effect transistors}, year = {2004}, abstract = {The optical, structural, and electrical properties of thin layers made from poly(3-hexylthiophene) (P3HT) samples of different molecular weights are presented. As reported in a previous paper by Kline et al., Adv. Mater 2003, 15, 1519, the mobilities of these layers are a strong function of the molecular weight, with the largest mobility found for the largest molecular weight. Atomic force microscopy studies reveal a complex polycrystalline morphology which changes considerably upon annealing. X-ray studies show the occurrence of a layered phase for all P3HT fractions, especially after annealing at 1.50 degreesC . However, there is no clear correlation between the differences in the transport properties and the data from structural investigations. In order to reveal the processes limiting the mobility in these layers, the transistor properties were investigated as a function of temperature. The mobility decreases continuously with increasing temperatures; with the same trend pronounced thermochromic effects of the P3HT films occur. Apparently, the polymer chains adopt a more twisted, disordered conformation at higher temperatures, leading to interchain transport barriers. We conclude that the backbone conformation of the majority of the bulk material rather than the crystallinity of the layer is the most crucial parameter controlling the charge transport in these P3HT layers. This interpretation is supported by the significant blue-shift of the solid-state absorption spectra with decreasing molecular weight, which is indicative of a larger distortion of the P3HT backbone in the low-molecular weight P3HT layers}, language = {en} } @article{BagnichUngerJaiseretal.2011, author = {Bagnich, Sergey A. and Unger, Th. and Jaiser, Frank and Neher, Dieter and Thesen, M. W. and Kr{\"u}ger, H.}, title = {Efficient green electrophosphorescence based on ambipolar nonconjugated polymers evaluation of transport and emission properties}, series = {Journal of applied physics}, volume = {110}, journal = {Journal of applied physics}, number = {3}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.3618681}, pages = {9}, year = {2011}, abstract = {New materials for polymer organic light-emitting diodes based on a polymer matrix doped with phosphorescent dyes are presented. The matrix system is based on a polystyrene backbone bearing either electron or hole transporting units at the 4-position of each repeat unit. Random copolymers and polymer blend systems of the homopolymers are prepared, both with 62 wt.\% electron transporting and 38 wt.\% hole transporting moieties. Adding a green electrophosphorescent dye to the polymer matrix leads to efficient electroluminescence with a maximum current efficiency of 35 cd/A and a maximum external quantum efficiency of up to 10\%. The mobilities of electrons and holes in the dye-doped copolymer, as measured by transient electroluminescence, are around 5 x 10(-5) and 5 x 10(-6) cm(2)/Vs, respectively, while the blend of the two homopolymers exhibits slightly lower mobilities of both types of carriers. Despite the pronounced imbalance of charge transport, the device performance is almost entirely limited by the phosphorescence efficiency of the dye, implying balanced flow of holes and electrons into the active region. Also, devices made with either the copolymer or the blend yielded very similar device efficiencies, despite the noticeable difference in electron and hole mobility. It is proposed that electrons are efficiently blocked at the interlayer and that the so-formed space charge assists the balanced injection of holes.}, language = {en} } @article{YangJaiserNeheretal.2004, author = {Yang, Xiao Hui and Jaiser, Frank and Neher, Dieter and Lawson, PaDreyia V. and Br{\´e}das, Jean-Luc and Zojer, Egbert and G{\"u}ntner, Roland and Scanduicci de Freitas, Patricia and Forster, Michael and Scherf, Ullrich}, title = {Suppression of the keto-emission in polyfluorene light-emitting diodes : Experiments and models}, issn = {1616-301X}, year = {2004}, abstract = {The spectral characteristics of polyfluorene (PF)-based light-emitting diodes (LEDs) containing a defined low concentration of either keto-defects or of the polymer poly(9.9-octylfuorene-co-benzothiadiazole) (F8BT) are preseneted. Both types of blend layers were tested in different device configurations with respect to the relative and absolute intensities of green blue emission components. It is shown that blending hole-transporting molecules into the emission layer at low concentration or incorporation of a suitable hole-transport layer reduces the green emission contribution in the electroluminescence (EL) spectrum of the PF:F8BT blend, which is similar to what is observed for the keto- containing PF layer. We conclude that the keto-defects in PF homopolymer layers mainly constitute weakly emissive electron traps, in agreement with the results of quantum-mechanical calculations}, language = {en} } @article{AlSa'diJaiserBagnichetal.2012, author = {Al-Sa'di, Mahmoud and Jaiser, Frank and Bagnich, Sergey A. and Unger, Thomas and Blakesley, James C. and Wilke, Andreas and Neher, Dieter}, title = {Electrical and optical simulations of a polymer-based phosphorescent organic light-emitting diode with high efficiency}, series = {Journal of polymer science : B, Polymer physics}, volume = {50}, journal = {Journal of polymer science : B, Polymer physics}, number = {22}, publisher = {Wiley-Blackwell}, address = {Hoboken}, issn = {0887-6266}, doi = {10.1002/polb.23158}, pages = {1567 -- 1576}, year = {2012}, abstract = {A comprehensive numerical device simulation of the electrical and optical characteristics accompanied with experimental measurements of a new highly efficient system for polymer-based light-emitting diodes doped with phosphorescent dyes is presented. The system under investigation comprises an electron transporter attached to a polymer backbone blended with an electronically inert small molecule and an iridium-based green phosphorescent dye which serves as both emitter and hole transporter. The device simulation combines an electrical and an optical model. Based on the known highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of all components as well as the measured electrical and optical characteristics of the devices, we model the emissive layer as an effective medium using the dye's HOMO as hole transport level and the polymer LUMO as electron transport level. By fine-tuning the injection barriers at the electron and hole-injecting contact, respectively, in simulated devices, unipolar device characteristics were fitted to the experimental data. Simulations using the so-obtained set of parameters yielded very good agreement to the measured currentvoltage, luminancevoltage characteristics, and the emission profile of entire bipolar light-emitting diodes, without additional fitting parameters. The simulation was used to gain insight into the physical processes and the mechanisms governing the efficiency of the organic light-emitting diode, including the position and extent of the recombination zone, carrier concentration profiles, and field distribution inside the device. The simulations show that the device is severely limited by hole injection, and that a reduction of the hole-injection barrier would improve the device efficiency by almost 50\%.}, language = {en} } @article{PranavHultzschMusiienkoetal.2023, author = {Pranav, Manasi and Hultzsch, Thomas and Musiienko, Artem and Sun, Bowen and Shukla, Atul and Jaiser, Frank and Shoaee, Safa and Neher, Dieter}, title = {Anticorrelated photoluminescence and free charge generation proves field-assisted exciton dissociation in low-offset PM6:Y5 organic solar cells}, series = {APL materials : high impact open access journal in functional materials science}, volume = {11}, journal = {APL materials : high impact open access journal in functional materials science}, number = {6}, publisher = {AIP Publishing}, address = {Melville}, issn = {2166-532X}, doi = {10.1063/5.0151580}, pages = {8}, year = {2023}, abstract = {Understanding the origin of inefficient photocurrent generation in organic solar cells with low energy offset remains key to realizing high-performance donor-acceptor systems. Here, we probe the origin of field-dependent free-charge generation and photoluminescence in wnon-fullereneacceptor (NFA)-based organic solar cells using the polymer PM6 and the NFA Y5-a non-halogenated sibling to Y6, with a smaller energetic offset to PM6. By performing time-delayed collection field (TDCF) measurements on a variety of samples with different electron transport layers and active layer thickness, we show that the fill factor and photocurrent are limited by field-dependent free charge generation in the bulk of the blend. We also introduce a new method of TDCF called m-TDCF to prove the absence of artifacts from non-geminate recombination of photogenerated and dark charge carriers near the electrodes. We then correlate free charge generation with steady-state photoluminescence intensity and find perfect anticorrelation between these two properties. Through this, we conclude that photocurrent generation in this low-offset system is entirely controlled by the field-dependent dissociation of local excitons into charge-transfer states. (c) 2023 Author(s).}, language = {en} } @article{TokmoldinVollbrechtHosseinietal.2021, author = {Tokmoldin, Nurlan and Vollbrecht, Joachim and Hosseini, Seyed Mehrdad and Sun, Bowen and Perdig{\´o}n-Toro, Lorena and Woo, Han Young and Zou, Yingping and Neher, Dieter and Shoaee, Safa}, title = {Explaining the fill-factor and photocurrent losses of nonfullerene acceptor-based solar cells by probing the long-range charge carrier diffusion and drift lengths}, series = {Advanced energy materials}, volume = {11}, journal = {Advanced energy materials}, number = {22}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6840}, doi = {10.1002/aenm.202100804}, pages = {9}, year = {2021}, abstract = {Organic solar cells (OSC) nowadays match their inorganic competitors in terms of current production but lag behind with regards to their open-circuit voltage loss and fill-factor, with state-of-the-art OSCs rarely displaying fill-factor of 80\% and above. The fill-factor of transport-limited solar cells, including organic photovoltaic devices, is affected by material and device-specific parameters, whose combination is represented in terms of the established figures of merit, such as theta and alpha. Herein, it is demonstrated that these figures of merit are closely related to the long-range carrier drift and diffusion lengths. Further, a simple approach is presented to devise these characteristic lengths using steady-state photoconductance measurements. This yields a straightforward way of determining theta and alpha in complete cells and under operating conditions. This approach is applied to a variety of photovoltaic devices-including the high efficiency nonfullerene acceptor blends-and show that the diffusion length of the free carriers provides a good correlation with the fill-factor. It is, finally, concluded that most state-of-the-art organic solar cells exhibit a sufficiently large drift length to guarantee efficient charge extraction at short circuit, but that they still suffer from too small diffusion lengths of photogenerated carriers limiting their fill factor.}, language = {en} } @article{KrohEllerSchoetzetal.2022, author = {Kroh, Daniel and Eller, Fabian and Sch{\"o}tz, Konstantin and Wedler, Stefan and Perdig{\´o}n-Toro, Lorena and Freychet, Guillaume and Wei, Qingya and D{\"o}rr, Maximilian and Jones, David and Zou, Yingping and Herzig, Eva M. and Neher, Dieter and K{\"o}hler, Anna}, title = {Identifying the signatures of intermolecular interactions in blends of PM6 with Y6 and N4 using absorption spectroscopy}, series = {Advanced functional materials}, volume = {32}, journal = {Advanced functional materials}, number = {44}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.202205711}, pages = {14}, year = {2022}, abstract = {In organic solar cells, the resulting device efficiency depends strongly on the local morphology and intermolecular interactions of the blend film. Optical spectroscopy was used to identify the spectral signatures of interacting chromophores in blend films of the donor polymer PM6 with two state-of-the-art nonfullerene acceptors, Y6 and N4, which differ merely in the branching point of the side chain. From temperature-dependent absorption and luminescence spectroscopy in solution, it is inferred that both acceptor materials form two types of aggregates that differ in their interaction energy. Y6 forms an aggregate with a predominant J-type character in solution, while for N4 molecules the interaction is predominantly in a H-like manner in solution and freshly spin-cast film, yet the molecules reorient with respect to each other with time or thermal annealing to adopt a more J-type interaction. The different aggregation behavior of the acceptor materials is also reflected in the blend films and accounts for the different solar cell efficiencies reported with the two blends.}, language = {en} } @article{KniepertPaulkePerdigonToroetal.2019, author = {Kniepert, Juliane and Paulke, Andreas and Perdig{\´o}n-Toro, Lorena and Kurpiers, Jona and Zhang, Huotian and Gao, Feng and Yuan, Jun and Zou, Yingping and Le Corre, Vincent M. and Koster, Lambert Jan Anton and Neher, Dieter}, title = {Reliability of charge carrier recombination data determined with charge extraction methods}, series = {Journal of applied physics}, volume = {126}, journal = {Journal of applied physics}, number = {20}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0021-8979}, doi = {10.1063/1.5129037}, pages = {15}, year = {2019}, abstract = {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.}, language = {en} } @article{WolffZuPaulkeetal.2017, author = {Wolff, Christian Michael and Zu, Fengshuo and Paulke, Andreas and Perdig{\´o}n-Toro, Lorena and Koch, Norbert and Neher, Dieter}, title = {Reduced Interface-Mediated Recombination for High Open-Circuit Voltages in CH3NH3PbI3 Solar Cells}, series = {Advanced materials}, volume = {29}, journal = {Advanced materials}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.201700159}, pages = {8}, year = {2017}, abstract = {Perovskite solar cells with all-organic transport layers exhibit efficiencies rivaling their counterparts that employ inorganic transport layers, while avoiding high-temperature processing. Herein, it is investigated how the choice of the fullerene derivative employed in the electron-transporting layer of inverted perovskite cells affects the open-circuit voltage (V-OC). It is shown that nonradiative recombination mediated by the electron-transporting layer is the limiting factor for the V-OC in the cells. By inserting an ultrathin layer of an insulating polymer between the active CH3NH3PbI3 perovskite and the fullerene, an external radiative efficiency of up to 0.3\%, a V-OC as high as 1.16 V, and a power conversion efficiency of 19.4\% are realized. The results show that the reduction of nonradiative recombination due to charge-blocking at the perovskite/organic interface is more important than proper level alignment in the search for ideal selective contacts toward high V-OC and efficiency.}, language = {en} } @article{SchwarzeSchellhammerOrtsteinetal.2019, author = {Schwarze, Martin and Schellhammer, Karl Sebastian and Ortstein, Katrin and Benduhn, Johannes and Gaul, Christopher and Hinderhofer, Alexander and Perdig{\´o}n-Toro, Lorena and Scholz, Reinhard and Kublitski, Jonas and Roland, Steffen and Lau, Matthias and Poelking, Carl and Andrienko, Denis and Cuniberti, Gianaurelio and Schreiber, Frank and Neher, Dieter and Vandewal, Koen and Ortmann, Frank and Leo, Karl}, title = {Impact of molecular quadrupole moments on the energy levels at organic heterojunctions}, series = {Nature Communications}, volume = {10}, journal = {Nature Communications}, publisher = {Nature Publ. Group}, address = {London}, issn = {2041-1723}, doi = {10.1038/s41467-019-10435-2}, pages = {9}, year = {2019}, abstract = {The functionality of organic semiconductor devices crucially depends on molecular energies, namely the ionisation energy and the electron affinity. Ionisation energy and electron affinity values of thin films are, however, sensitive to film morphology and composition, making their prediction challenging. In a combined experimental and simulation study on zinc-phthalocyanine and its fluorinated derivatives, we show that changes in ionisation energy as a function of molecular orientation in neat films or mixing ratio in blends are proportional to the molecular quadrupole component along the p-p-stacking direction. We apply these findings to organic solar cells and demonstrate how the electrostatic interactions can be tuned to optimise the energy of the charge-transfer state at the donor-acceptor interface and the dissociation barrier for free charge carrier generation. The confirmation of the correlation between interfacial energies and quadrupole moments for other materials indicates its relevance for small molecules and polymers.}, language = {en} } @article{ColladoFregosoPuglieseWojciketal.2019, author = {Collado-Fregoso, Elisa and Pugliese, Silvina N. and Wojcik, Mariusz and Benduhn, Johannes and Bar-Or, Eyal and Perdig{\´o}n-Toro, Lorena and H{\"o}rmann, Ulrich and Spoltore, Donato and Vandewal, Koen and Hodgkiss, Justin M. and Neher, Dieter}, title = {Energy-gap law for photocurrent generation in fullerene-based organic solar cells}, series = {Journal of the American Chemical Society}, volume = {141}, journal = {Journal of the American Chemical Society}, number = {6}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/jacs.8b09820}, pages = {2329 -- 2341}, year = {2019}, abstract = {The involvement of charge-transfer (CT) states in the photogeneration and recombination of charge carriers has been an important focus of study within the organic photovoltaic community. In this work, we investigate the molecular factors determining the mechanism of photocurrent generation in low-donor-content organic solar cells, where the active layer is composed of vacuum-deposited C-60 and small amounts of organic donor molecules. We find a pronounced decline of all photovoltaic parameters with decreasing CT state energy. Using a combination of steady-state photocurrent measurements and time-delayed collection field experiments, we demonstrate that the power conversion efficiency, and more specifically, the fill factor of these devices, is mainly determined by the bias dependence of photocurrent generation. By combining these findings with the results from ultrafast transient absorption spectroscopy, we show that blends with small CT energies perform poorly because of an increased nonradiative CT state decay rate and that this decay obeys an energy-gap law. Our work challenges the common view that a large energy offset at the heterojunction and/or the presence of fullerene clusters guarantee efficient CT dissociation and rather indicates that charge generation benefits from high CT state energies through a slower decay to the ground state.}, language = {en} }