TY - JOUR A1 - Zuo, Guangzheng A1 - Shoaee, Safa A1 - Kemerink, Martijn A1 - Neher, Dieter T1 - General rules for the impact of energetic disorder and mobility on nongeminate recombination in phase-separated organic solar cells JF - Physical review applied N2 - State-of-the-art organic solar cells exhibit power conversion efficiencies of 18% and above. These devices benefit from the suppression of free charge recombination with regard to the Langevin limit of charge encounter in a homogeneous medium. It is recognized that the main cause of suppressed free charge recombination is the reformation and resplitting of charge-transfer (CT) states at the interface between donor and acceptor domains. Here, we use kinetic Monte Carlo simulations to understand the interplay between free charge motion and recombination in an energetically disordered phase-separated donor-acceptor blend. We identify conditions for encounter-dominated and resplitting-dominated recombination. In the former regime, recombination is proportional to mobility for all parameters tested and only slightly reduced with respect to the Langevin limit. In contrast, mobility is not the decisive parameter that determines the nongeminate recombination coefficient, k(2), in the latter case, where k2 is a sole function of the morphology, CT and charge-separated (CS) energetics, and CT-state decay properties. Our simulations also show that free charge encounter in the phase-separated disordered blend is determined by the average mobility of all carriers, while CT reformation and resplitting involves mostly states near the transport energy. Therefore, charge encounter is more affected by increased disorder than the resplitting of the CT state. As a consequence, for a given mobility, larger energetic disorder, in combination with a higher hopping rate, is preferred. These findings have implications for the understanding of suppressed recombination in solar cells with nonfullerene acceptors, which are known to exhibit lower energetic disorder than that of fullerenes. Y1 - 2021 U6 - https://doi.org/10.1103/PhysRevApplied.16.034027 SN - 2331-7019 VL - 16 IS - 3 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Zu, Fengshuo A1 - Wolff, Christian Michael A1 - Ralaiarisoa, Maryline A1 - Amsalem, Patrick A1 - Neher, Dieter A1 - Koch, Norbert T1 - Unraveling the Electronic Properties of Lead Halide Perovskites with Surface Photovoltage in Photoemission Studies JF - ACS applied materials & interfaces N2 - The tremendous success of metal-halide perovskites, especially in the field of photovoltaics, has triggered a substantial number of studies in understanding their optoelectronic properties. However, consensus regarding the electronic properties of these perovskites is lacking due to a huge scatter in the reported key parameters, such as work function (Φ) and valence band maximum (VBM) values. Here, we demonstrate that the surface photovoltage (SPV) is a key phenomenon occurring at the perovskite surfaces that feature a non-negligible density of surface states, which is more the rule than an exception for most materials under study. With ultraviolet photoelectron spectroscopy (UPS) and Kelvin probe, we evidence that even minute UV photon fluxes (500 times lower than that used in typical UPS experiments) are sufficient to induce SPV and shift the perovskite Φ and VBM by several 100 meV compared to dark. By combining UV and visible light, we establish flat band conditions (i.e., compensate the surface-state-induced surface band bending) at the surface of four important perovskites, and find that all are p-type in the bulk, despite a pronounced n-type surface character in the dark. The present findings highlight that SPV effects must be considered in all surface studies to fully understand perovskites’ photophysical properties. KW - lead halide perovskite films KW - ultraviolet photoelectron spectroscopy KW - Kelvin probe KW - surface band bending KW - surface photovoltage KW - surface states Y1 - 2019 U6 - https://doi.org/10.1021/acsami.9b05293 SN - 1944-8244 SN - 1944-8252 VL - 11 IS - 24 SP - 21578 EP - 21583 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zu, Fengshuo A1 - Schultz, Thorsten A1 - Wolff, Christian Michael A1 - Shin, Dongguen A1 - Frohloff, Lennart A1 - Neher, Dieter A1 - Amsalem, Patrick A1 - Koch, Norbert T1 - Position-locking of volatile reaction products by atmosphere and capping layers slows down photodecomposition of methylammonium lead triiodide perovskite JF - RSC Advances N2 - The remarkable progress of metal halide perovskites in photovoltaics has led to the power conversion efficiency approaching 26%. However, practical applications of perovskite-based solar cells are challenged by the stability issues, of which the most critical one is photo-induced degradation. Bare CH3NH3PbI3 perovskite films are known to decompose rapidly, with methylammonium and iodine as volatile species and residual solid PbI2 and metallic Pb, under vacuum under white light illumination, on the timescale of minutes. We find, in agreement with previous work, that the degradation is non-uniform and proceeds predominantly from the surface, and that illumination under N-2 and ambient air (relative humidity 20%) does not induce substantial degradation even after several hours. Yet, in all cases the release of iodine from the perovskite surface is directly identified by X-ray photoelectron spectroscopy. This goes in hand with a loss of organic cations and the formation of metallic Pb. When CH3NH3PbI3 films are covered with a few nm thick organic capping layer, either charge selective or non-selective, the rapid photodecomposition process under ultrahigh vacuum is reduced by more than one order of magnitude, and becomes similar in timescale to that under N-2 or air. We conclude that the light-induced decomposition reaction of CH3NH3PbI3, leading to volatile methylammonium and iodine, is largely reversible as long as these products are restrained from leaving the surface. This is readily achieved by ambient atmospheric pressure, as well as a thin organic capping layer even under ultrahigh vacuum. In addition to explaining the impact of gas pressure on the stability of this perovskite, our results indicate that covalently "locking" the position of perovskite components at the surface or an interface should enhance the overall photostability. Y1 - 2020 U6 - https://doi.org/10.1039/d0ra03572f SN - 2046-2069 VL - 10 IS - 30 SP - 17534 EP - 17542 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Zu, Fengshuo A1 - Amsalem, Patrick A1 - Egger, David A. A1 - Wang, Rongbin A1 - Wolff, Christian Michael A1 - Fang, Honghua A1 - Loi, Maria Antonietta A1 - Neher, Dieter A1 - Kronik, Leeor A1 - Duhm, Steffen A1 - Koch, Norbert T1 - Constructing the Electronic Structure of CH3NH3PbI3 and CH3NH3PbBr3 Perovskite Thin Films from Single-Crystal Band Structure Measurements JF - The journal of physical chemistry letters N2 - Photovoltaic cells based on halide perovskites, possessing remarkably high power conversion efficiencies have been reported. To push the development of such devices further, a comprehensive and reliable understanding of their electronic properties is essential but presently not available. To provide a solid foundation for understanding the electronic properties of polycrystalline thin films, we employ single-crystal band structure data from angle-resolved photoemission measurements. For two prototypical perovskites (CH3NH3PbBr3 and CH3NH3PbI3), we reveal the band dispersion in two high-symmetry directions and identify the global valence band maxima. With these benchmark data, we construct "standard" photoemission spectra from polycrystalline thin film samples and resolve challenges discussed in the literature for determining the valence band onset with high reliability. Within the framework laid out here, the consistency of relating the energy level alignment in perovskite-based photovoltaic and optoelectronic devices with their functional parameters is substantially enhanced. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpclett.8b03728 SN - 1948-7185 VL - 10 IS - 3 SP - 601 EP - 609 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zhang, Shanshan A1 - Stolterfoht, Martin A1 - Armin, Ardalan A1 - Lin, Qianqian A1 - Zu, Fengshuo A1 - Sobus, Jan A1 - Jin, Hui A1 - Koch, Norbert A1 - Meredith, Paul A1 - Burn, Paul L. A1 - Neher, Dieter T1 - Interface Engineering of Solution-Processed Hybrid Organohalide Perovskite Solar Cells JF - ACS applied materials & interfaces N2 - Engineering the interface between the perovskite absorber and the charge-transporting layers has become an important method for improving the charge extraction and open-circuit voltage (V-OC) of hybrid perovskite solar cells. Conjugated polymers are particularly suited to form the hole-transporting layer, but their hydrophobicity renders it difficult to solution-process the perovskite absorber on top. Herein, oxygen plasma treatment is introduced as a simple means to change the surface energy and work function of hydrophobic polymer interlayers for use as p-contacts in perovskite solar cells. We find that upon oxygen plasma treatment, the hydrophobic surfaces of different prototypical p-type polymers became sufficiently hydrophilic to enable subsequent perovskite junction processing. In addition, the oxygen plasma treatment also increased the ionization potential of the polymer such that it became closer to the valance band energy of the perovskite. It was also found that the oxygen plasma treatment could increase the electrical conductivity of the p-type polymers, facilitating more efficient charge extraction. On the basis of this concept, inverted MAPbI(3) perovskite devices with different oxygen plasma-treated polymers such as P3HT, P3OT, polyTPD, or PTAA were fabricated with power conversion efficiencies of up to 19%. KW - organohalide lead perovskites KW - solar cells KW - surface wetting KW - work function KW - oxygen plasma KW - transport layer Y1 - 2018 U6 - https://doi.org/10.1021/acsami.8b02503 SN - 1944-8244 VL - 10 IS - 25 SP - 21681 EP - 21687 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zhang, Shanshan A1 - Hosseini, Seyed Mehrdad A1 - Gunder, Rene A1 - Petsiuk, Andrei A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Shoaee, Safa A1 - Meredith, Paul A1 - Schorr, Susan A1 - Unold, Thomas A1 - Burn, Paul L. A1 - Neher, Dieter A1 - Stolterfoht, Martin T1 - The Role of Bulk and Interface Recombination in High-Efficiency Low-Dimensional Perovskite Solar Cells JF - Advanced materials N2 - 2D Ruddlesden-Popper perovskite (RPP) solar cells have excellent environmental stability. However, the power conversion efficiency (PCE) of RPP cells remains inferior to 3D perovskite-based cells. Herein, 2D (CH3(CH2)(3)NH3)(2)(CH3NH3)(n-1)PbnI3n+1 perovskite cells with different numbers of [PbI6](4-) sheets (n = 2-4) are analyzed. Photoluminescence quantum yield (PLQY) measurements show that nonradiative open-circuit voltage (V-OC) losses outweigh radiative losses in materials with n > 2. The n = 3 and n = 4 films exhibit a higher PLQY than the standard 3D methylammonium lead iodide perovskite although this is accompanied by increased interfacial recombination at the top perovskite/C-60 interface. This tradeoff results in a similar PLQY in all devices, including the n = 2 system where the perovskite bulk dominates the recombination properties of the cell. In most cases the quasi-Fermi level splitting matches the device V-OC within 20 meV, which indicates minimal recombination losses at the metal contacts. The results show that poor charge transport rather than exciton dissociation is the primary reason for the reduction in fill factor of the RPP devices. Optimized n = 4 RPP solar cells had PCEs of 13% with significant potential for further improvements. KW - 2D perovskites KW - interface recombination KW - perovskite solar cells KW - photoluminescence KW - V-OC loss Y1 - 2019 U6 - https://doi.org/10.1002/adma.201901090 SN - 0935-9648 SN - 1521-4095 VL - 31 IS - 30 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Zerson, Mario A1 - Neumann, Martin A1 - Steyrleuthner, Robert A1 - Neher, Dieter A1 - Magerle, Robert T1 - Surface Structure of Semicrystalline Naphthalene Diimide-Bithiophene Copolymer Films Studied with Atomic Force Microscopy JF - Macromolecules : a publication of the American Chemical Society Y1 - 2016 U6 - https://doi.org/10.1021/acs.macromol.6b00988 SN - 0024-9297 SN - 1520-5835 VL - 49 SP - 6549 EP - 6557 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Zentel, Rudolf A1 - Behl, Marc A1 - Neher, Dieter A1 - Zen, Achmad A1 - Lucht, Sylvia T1 - Nanostructured polytriarylamines : orientation layers for polyfluorene Y1 - 2004 SN - 0065-7727 ER - TY - JOUR A1 - Zen, Achmad A1 - Saphiannikova, Marina A1 - Neher, Dieter A1 - Grenzer, Jörg A1 - Grigorian, Souren A. A1 - Pietsch, Ullrich A1 - Asawapirom, Udom A1 - Janietz, Silvia A1 - Scherf, Ullrich A1 - Lieberwirth, Ingo A1 - Wegner, Gerhard T1 - Effect of molecular weight on the structure and crystallinity of poly(3-hexylthiophene) N2 - Recently, two different groups have reported independently that the mobility of field-effect transistors made from regioregular poly(3-hexylthiophene) (P3HT) increases strongly with molecular weight. Two different models were presented: one proposing carrier trapping at grain boundaries and the second putting emphasis on the conformation and packing of the polymer chains in the thin layers for different molecular weights. Here, we present the results of detailed investigations of powders and thin films of deuterated P3HT fractions with different molecular weight. For powder samples, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were used to investigate the structure and crystallization behavior of the polymers. The GPC investigations show that all weight fractions possess a rather broad molecular weight distribution. DSC measurements reveal a strong decrease of the crystallization temperature and, most important, a significant decrease of the degree of crystallinity with decreasing molecular weight. To study the structure of thin layers in lateral and vertical directions, both transmission electron microscopy (TEM) and X-ray grazing incidence diffraction (GID) were utilized. These methods show that thin layers of the low molecular weight fraction consist of well-defined crystalline domains embedded in a disordered matrix. We propose that the transport properties of layers prepared from fractions of poly(3-hexylthiophene) with different molecular weight are largely determined by the crystallinity of the samples and not by the perfection of the packing of the chains in the individual crystallites Y1 - 2006 UR - http://pubs.acs.org/doi/full/10.1021/ma0521349 U6 - https://doi.org/10.1021/Ma0521349 ER - TY - JOUR A1 - Zen, Achmad A1 - Saphiannikova, Marina A1 - Neher, Dieter A1 - Asawapirom, Udom A1 - Scherf, Ullrich T1 - Comparative study of the field-effect mobility of a copolymer and a binary blend based on poly(3- alkylthiophene)s N2 - The performance of highly soluble regioregular poly[ (3-hexylthiophene)-co-(3-octylthiophetie)] (P3HTOT) as a semiconducting material in organic field-effect transistors (OFETs) is presented in comparison to that of the corresponding homopolymers. Transistors made from as-prepared layers of P3HTOT exhibit a mobility of ca. 7 x 10(-3) cm(2) V-1 s(-1), which is comparable to the performance of transistors made from as-prepared poly(3-hexylthiophene) (P3HT) and almost 6 times larger than the mobility of transistors prepared with poly(3-octylthiophene) (P3OT). On the other hand, the solubility parameter delta(p) of P3HTOT is close to that of the highly soluble P3OT. Moreover, compared to a physical blend of poly(3-hexylthiophene) and poly(3-octylthiophene), the mobility of P3HTOT devices is almost twice as large and the performance does not degrade upon annealing at elevated temperatures. Therefore, the copolymer approach outlined here may be one promising step toward an optimum balance between a Sufficient processability of the polymers from common organic solvents, a high solid state order, and applicable OFET performances Y1 - 2005 SN - 0897-4756 ER - TY - JOUR A1 - Zen, Achmad A1 - Pflaum, J. A1 - Hirschmann, S. A1 - Zhuang, W. A1 - Jaiser, Frank A1 - Asawapirom, Udom A1 - Rabe, J. P. A1 - Scherf, Ullrich A1 - Neher, Dieter T1 - Effect of molecular weight and annealing of poly (3-hexylthiophene)s on the performance of organic field-effect transistors N2 - 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 Y1 - 2004 ER - TY - JOUR A1 - Zen, Achmad A1 - Neher, Dieter A1 - Silmy, Kamel A1 - Hollander, A. A1 - Asawapirom, Udom A1 - Scherf, Ullrich T1 - Improving the performance of organic field effect transistor by optimizing the gate insulator surface N2 - The effect of oxygen plasma treatment and/or silanization with hexamethyldisilazane (HMDS) on the surface chemistry and the morphology of the SiO2-gate insulator were studied with respect to the performance of organic field effect transistors. Using X-ray photoelectron spectroscopy (XPS), it is shown that silanization leads to the growth of a polysiloxane interfacial layer and that longer silanization times increase the thickness of this layer. Most important, silanization reduces the signal from surface contaminations such as oxidized hydrocarbon molecules. In fact, the lowest concentration of these contaminations was found after a combined oxygen plasma/silanization treatment. The results of these investigations were correlated with the characteristic device parameters of polymer field effect transistors with poly(3-hexylthiophene)s as the semiconducting layer. We found that the field effect mobility correlates with the concentration of contaminations as measured by XPS. We, finally, demonstrate that silanization significantly improves the operational stability of the device in air compared to the untreated devices Y1 - 2005 ER - TY - JOUR A1 - Zen, Achmad A1 - Neher, Dieter A1 - Bauer, C. A1 - Asawapirom, Udom A1 - Scherf, Ullrich A1 - Hagen, R. A1 - Kostromine, S. A1 - Mahrt, R. F. T1 - Polarization-sensitive photoconductivity in aligned polyfluorene layers Y1 - 2002 ER - TY - JOUR A1 - Zen, Achmad A1 - Bilge, Askin A1 - Galbrecht, Frank A1 - Alle, Ronald A1 - Meerholz, Klaus A1 - Grenzer, Jörg A1 - Neher, Dieter A1 - Scherf, Ullrich A1 - Farrell, Tony T1 - Solution processable organic field-effect transistors utilizing an alpha,alpha '-dihexylpentathiophene- based swivel cruciform Y1 - 2006 UR - http://pubs.acs.org/doi/full/10.1021/ja0573357 U6 - https://doi.org/10.1021/Ja0573357 ER - TY - JOUR A1 - Yin, Chunhong A1 - Schubert, Marcel A1 - Stiller, Burkhard A1 - Castellani, Mauro A1 - Neher, Dieter A1 - Kumke, Michael Uwe A1 - Hörhold, Hans-Heinrich T1 - Tuning of the excited-state properties and photovoltaic performance in PPV-based polymer blends Y1 - 2008 U6 - https://doi.org/10.1021/Jp803977k ER - TY - JOUR A1 - Ye, Fangyuan A1 - Zhang, Shuo A1 - Warby, Jonathan A1 - Wu, Jiawei A1 - Gutierrez-Partida, Emilio A1 - Lang, Felix A1 - Shah, Sahil A1 - Saglamkaya, Elifnaz A1 - Sun, Bowen A1 - Zu, Fengshuo A1 - Shoai, Safa A1 - Wang, Haifeng A1 - Stiller, Burkhard A1 - Neher, Dieter A1 - Zhu, Wei-Hong A1 - Stolterfoht, Martin A1 - Wu, Yongzhen T1 - Overcoming C₆₀-induced interfacial recombination in inverted perovskite solar cells by electron-transporting carborane JF - Nature Communications N2 - Inverted perovskite solar cells still suffer from significant non-radiative recombination losses at the perovskite surface and across the perovskite/C₆₀ interface, limiting the future development of perovskite-based single- and multi-junction photovoltaics. Therefore, more effective inter- or transport layers are urgently required. To tackle these recombination losses, we introduce ortho-carborane as an interlayer material that has a spherical molecular structure and a three-dimensional aromaticity. Based on a variety of experimental techniques, we show that ortho-carborane decorated with phenylamino groups effectively passivates the perovskite surface and essentially eliminates the non-radiative recombination loss across the perovskite/C₆₀ interface with high thermal stability. We further demonstrate the potential of carborane as an electron transport material, facilitating electron extraction while blocking holes from the interface. The resulting inverted perovskite solar cells deliver a power conversion efficiency of over 23% with a low non-radiative voltage loss of 110 mV, and retain >97% of the initial efficiency after 400 h of maximum power point tracking. Overall, the designed carborane based interlayer simultaneously enables passivation, electron-transport and hole-blocking and paves the way toward more efficient and stable perovskite solar cells. Y1 - 2022 U6 - https://doi.org/10.1038/s41467-022-34203-x SN - 2041-1723 VL - 13 PB - Springer Nature CY - London ER - TY - JOUR A1 - Ye, Fangyuan A1 - Zhang, Shuo A1 - Warby, Jonathan A1 - Wu, Jiawei A1 - Gutierrez-Partida, Emilio A1 - Lang, Felix A1 - Shah, Sahil A1 - Saglamkaya, Elifnaz A1 - Sun, Bowen A1 - Zu, Fengshuo A1 - Shoaee, Safa A1 - Wang, Haifeng A1 - Stiller, Burkhard A1 - Neher, Dieter A1 - Zhu, Wei-Hong A1 - Stolterfoht, Martin A1 - Wu, Yongzhen T1 - Overcoming C-60-induced interfacial recombination in inverted perovskite solar cells by electron-transporting carborane JF - Nature Communications N2 - Inverted perovskite solar cells still suffer from significant non-radiative recombination losses at the perovskite surface and across the perovskite/C-60 interface, limiting the future development of perovskite-based single- and multi-junction photovoltaics. Therefore, more effective inter- or transport layers are urgently required. To tackle these recombination losses, we introduce ortho-carborane as an interlayer material that has a spherical molecular structure and a three-dimensional aromaticity. Based on a variety of experimental techniques, we show that ortho-carborane decorated with phenylamino groups effectively passivates the perovskite surface and essentially eliminates the non-radiative recombination loss across the perovskite/C-60 interface with high thermal stability. We further demonstrate the potential of carborane as an electron transport material, facilitating electron extraction while blocking holes from the interface. The resulting inverted perovskite solar cells deliver a power conversion efficiency of over 23% with a low non-radiative voltage loss of 110mV, and retain >97% of the initial efficiency after 400h of maximum power point tracking. Overall, the designed carborane based interlayer simultaneously enables passivation, electron-transport and hole-blocking and paves the way toward more efficient and stable perovskite solar cells. Effective transport layers are essential to suppress non-radiative recombination losses. Here, the authors introduce phenylamino-functionalized ortho-carborane as an interfacial layer, and realise inverted perovskite solar cells with efficiency of over 23% and operational stability of T97=400h. Y1 - 2022 U6 - https://doi.org/10.1038/s41467-022-34203-x SN - 2041-1723 VL - 13 IS - 1 PB - Nature Publishing Group CY - London ER - TY - JOUR A1 - Yang, Xiaohui A1 - Müller, David C. A1 - Neher, Dieter A1 - Meerholz, Klaus T1 - Highly efficient polymeric electrophosphorescent diodes N2 - Polymeric electrophosphorescent LEDs with internal quantum efficiencies approaching unity have been fabricated. Such performance levels are previously unknown for OLEDs. The key to this success is redox chemically doped oxetane- crosslinkable hole-transporting layers with multilayer capability (see figure). They improve hole injection and act as electron-blocking layers, without the need to include exciton-or hole-blocking layers Y1 - 2006 UR - 1960 = DOI: 10.1002/adma.200501867 ER - TY - JOUR A1 - Yang, Xiao Hui A1 - Jaiser, Frank A1 - Stiller, Burkhard A1 - Neher, Dieter A1 - Galbrecht, Frank A1 - Scherf, Ullrich T1 - Efficient polymer electrophosphoreseent devices with interfacial layers JF - Advanced functional materials N2 - It is shown that several polymers can form insoluble interfacial layers on a poly (ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) layer after annealing of the double-layer structure. The thickness of the interlayer is dependent on the characteristics of the underlying PEDOT.PSS and the molecular weight of the polymers. It is further shown that the electronic structures of the interlayer polymers have a significant effect on the properties of red-light-emitting polymer-based electrophosphorescent devices. Upon increasing the highest occupied molecular orbital and lowest unoccupied molecular orbital positions, a significant increase in current density and device efficiency is observed. This is attributed to efficient blocking of electrons in combination with direct injection of holes from the interlayer to the phosphorescent dye. Upon proper choice of the interlayer polymer, efficient red, polymer-based electrophosphorescent devices with a peak luminance efficiency of 5.5 cd A(-1) (external quantum efficiency = 6 %) and a maximum power-conversion efficiency of 5 Im W-1 can be realized. Y1 - 2006 U6 - https://doi.org/10.1002/adfm.200500834 SN - 1616-301X SN - 1616-3028 VL - 16 IS - 16 SP - 2156 EP - 2162 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Yang, Xiao Hui A1 - Jaiser, Frank A1 - Neher, Dieter A1 - Lawson, PaDreyia V. A1 - Brédas, Jean-Luc A1 - Zojer, Egbert A1 - Güntner, Roland A1 - Scanduicci de Freitas, Patricia A1 - Forster, Michael A1 - Scherf, Ullrich T1 - Suppression of the keto-emission in polyfluorene light-emitting diodes : Experiments and models N2 - 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 Y1 - 2004 SN - 1616-301X ER - TY - JOUR A1 - Yang, X. H. A1 - Neher, Dieter A1 - Hertel, D. A1 - Daubler, T. K. T1 - Highly efficient single-layer polymer electrophosphorescent devices N2 - A commercially available Ir complex has been employed for the preparation of highly efficient (see Figure) single-layer phosphorescent polymer light,emitting diodes by use of appropriate thermal treatment and proper adjustment of the layer composition. These devices exhibit essentially no dependence of the driving field on the concentration of the Ir complex, suggesting that the build-up of space-charge in the layer is insignificant Y1 - 2004 SN - 0935-9648 ER - TY - JOUR A1 - Yang, X. H. A1 - Neher, Dieter T1 - Polymer electrophosphorescence devices with high power conversion efficiencies N2 - We demonstrate efficient single-layer polymer phosphorescent light-emitting devices based on a green-emitting iridium complex and a polymer host co-doped with electron-transporting and hole-transporting molecules. These devices can be operated at relatively low voltages, resulting in a power conversion efficiency of up to 24 lm/W at luminous efficiencies exceeding 30 cd/A. The overall performances of these devices suggest that efficient electrophosphorescent devices with acceptable operating voltages can be achieved in very simple device structures fabricated by spin coating. (C) 2004 American Institute of Physics Y1 - 2004 SN - 0003-6951 ER - TY - JOUR A1 - Yang, X. H. A1 - Jaiser, Frank A1 - Klinger, S A1 - Neher, Dieter T1 - Blue polymer electrophosphorescent devices with different electron-transporting oxadiazoles N2 - We report that the performances of blue polymer electrophosphorescent devices are crucially depending on the choice of the electron transporting material incorporated into the emissive layer. Devices with 1,3-bis[(4-tert- butylphenyl)-1,3,4-oxidiazolyl]phenylene (OXD-7) doped at similar to 40 wt% into a poly(vinylcarbazole) matrix exhibited significantly higher efficiencies than those with 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), yielding maximum luminous and power efficiency values of 18.2 Cd/A and 8.8 lm/W, respectively. Time resolved photoluminescence measurements revealed a long lifetime phosphorescence component in layers with PBD, which we assign to significant triplet harvesting by this electron-transporting component. (c) 2006 American Institute of Physics Y1 - 2006 UR - http://scitation.aip.org/getpdf/servlet/ GetPDFServlet?filetype=pdf&id=APPLAB000088000002021107000001&idtype=cvips&doi=10.1063/1.2162693&prog=normal U6 - https://doi.org/10.1063/1.2162693 ER - TY - JOUR A1 - Xu, Jingsan A1 - Shalom, Menny A1 - Piersimoni, Fortunato A1 - Antonietti, Markus A1 - Neher, Dieter A1 - Brenner, Thomas J. K. T1 - Color-Tunable Photoluminescence and NIR Electroluminescence in Carbon Nitride Thin Films and Light-Emitting Diodes JF - Advanced optical materials Y1 - 2015 U6 - https://doi.org/10.1002/adom.201500019 SN - 2195-1071 VL - 3 IS - 7 SP - 913 EP - 917 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Xu, Jingsan A1 - Brenner, Thomas J. K. A1 - Chen, Zupeng A1 - Neher, Dieter A1 - Antonietti, Markus A1 - Shalom, Menny T1 - Upconversion-agent induced improvement of g-C3N4 photocatalyst under visible light JF - ACS applied materials & interfaces N2 - Herein, we report the use of upconversion agents to modify graphite carbon nitride (g-C3N4) by direct thermal condensation of a mixture of ErCl3 center dot 6H(2)O and the supramolecular precursor cyanuric acid-melamine. We show the enhancement of g-C3N4 photoactivity after Er3+ doping by monitoring the photodegradation of Rhodamine B dye under visible light. The contribution of the upconversion agent is demonstrated by measurements using only a red laser. The Er3+ doping alters both the electronic and the chemical properties of g-C3N4. The Er3+ doping reduces emission intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes. KW - metal-free photocatalysis KW - upconversion KW - carbon nitride KW - RhB photodegradation Y1 - 2014 U6 - https://doi.org/10.1021/am5051263 SN - 1944-8244 VL - 6 IS - 19 SP - 16481 EP - 16486 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Xu, Jingsan A1 - Brenner, Thomas J. K. A1 - Chabanne, Laurent A1 - Neher, Dieter A1 - Antonietti, Markus A1 - Shalom, Menny T1 - Liquid-Based growth of polymeric carbon nitride layers and their use in a mesostructured polymer solar cell with V-oc exceeding 1 V JF - Journal of the American Chemical Society N2 - Herein we report a general liquid-mediated pathway for the growth of continuous polymeric carbon nitride (C3N4) thin films. The deposition method consists of the use of supramolecular complexes that transform to the liquid state before direct thermal condensation into C3N4 solid films. The resulting films exhibit continuous porous C3N4 networks on various substrates. Moreover, the optical absorption can be easily tuned to cover the solar spectrum by the insertion of an additional molecule into the starting complex. The strength of the deposition method is demonstrated by the use of the C3N4 layer as the electron acceptor in a polymer solar cell that exhibits a remarkable open-circuit voltage exceeding 1 V. The easy, safe, and direct synthesis of carbon nitride in a continuous layered architecture on different functional substrates opens new possibilities for the fabrication of many energy-related devices. Y1 - 2014 U6 - https://doi.org/10.1021/ja508329c SN - 0002-7863 VL - 136 IS - 39 SP - 13486 EP - 13489 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Würfel, Uli A1 - Perdigon-Toro, Lorena A1 - Kurpiers, Jona A1 - Wolff, Christian Michael A1 - Caprioglio, Pietro A1 - Rech, Jeromy James A1 - Zhu, Jingshuai A1 - Zhan, Xiaowei A1 - You, Wei A1 - Shoaee, Safa A1 - Neher, Dieter A1 - Stolterfoht, Martin T1 - Recombination between Photogenerated and Electrode-Induced Charges Dominates the Fill Factor Losses in Optimized Organic Solar Cells JF - The journal of physical chemistry letters N2 - Charge extraction in organic solar cells (OSCs) is commonly believed to be limited by bimolecular recombination of photogenerated charges. However, the fill factor of OSCs is usually almost entirely governed by recombination processes that scale with the first order of the light intensity. This linear loss was often interpreted to be a consequence of geminate or trap-assisted recombination. Numerical simulations show that this linear dependence is a direct consequence of the large amount of excess dark charge near the contact. The first-order losses increase with decreasing mobility of minority carriers, and we discuss the impact of several material and device parameters on this loss mechanism. This work highlights that OSCs are especially vulnerable to injected charges as a result of their poor charge transport properties. This implies that dark charges need to be better accounted for when interpreting electro-optical measurements and charge collection based on simple figures of merit. Y1 - 2019 U6 - https://doi.org/10.1021/acs.jpclett.9b01175 SN - 1948-7185 VL - 10 IS - 12 SP - 3473 EP - 3480 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Würfel, Uli A1 - Neher, Dieter A1 - Spies, Annika A1 - Albrecht, Steve T1 - Impact of charge transport on current-voltage characteristics and power-conversion efficiency of organic solar cells JF - Nature Communications N2 - This work elucidates the impact of charge transport on the photovoltaic properties of organic solar cells. Here we show that the analysis of current-voltage curves of organic solar cells under illumination with the Shockley equation results in values for ideality factor, photo-current and parallel resistance, which lack physical meaning. Drift-diffusion simulations for a wide range of charge-carrier mobilities and illumination intensities reveal significant carrier accumulation caused by poor transport properties, which is not included in the Shockley equation. As a consequence, the separation of the quasi Fermi levels in the organic photoactive layer (internal voltage) differs substantially from the external voltage for almost all conditions. We present a new analytical model, which considers carrier transport explicitly. The model shows excellent agreement with full drift-diffusion simulations over a wide range of mobilities and illumination intensities, making it suitable for realistic efficiency predictions for organic solar cells. Y1 - 2015 U6 - https://doi.org/10.1038/ncomms7951 SN - 2041-1723 VL - 6 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Wolff, Christian Michael A1 - Zu, Fengshuo A1 - Paulke, Andreas A1 - Toro, Lorena Perdigon A1 - Koch, Norbert A1 - Neher, Dieter T1 - Reduced Interface-Mediated Recombination for High Open-Circuit Voltages in CH3NH3PbI3 Solar Cells JF - Advanced materials N2 - 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. KW - electron-transport layers KW - nonradiative recombination KW - open-circuit voltage KW - perovskite solar cells Y1 - 2017 U6 - https://doi.org/10.1002/adma.201700159 SN - 0935-9648 SN - 1521-4095 VL - 29 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Wilson, J. N. A1 - Steffen, W. A1 - McKenzie, T. G. A1 - Lieser, G. A1 - Oda, Masao A1 - Neher, Dieter A1 - Bunz, Uwe H. F. T1 - Chiroptcial properties of poly(p-phenyleneethynylene) copolymers in thin films : large g-values Y1 - 2002 ER - TY - JOUR A1 - Wang, Qiong A1 - Smith, Joel A. A1 - Skroblin, Dieter A1 - Steele, Julian A. A1 - Wolff, Christian M. A1 - Caprioglio, Pietro A1 - Stolterfoht, Martin A1 - Köbler, Hans A1 - Turren-Cruz, Silver-Hamill A1 - Li, Meng A1 - Gollwitzer, Christian A1 - Neher, Dieter A1 - Abate, Antonio T1 - Managing phase purities and crystal orientation for high-performance and photostable cesium lead halide perovskite solar cells JF - Solar RRL N2 - Inorganic perovskites with cesium (Cs+) as the cation have great potential as photovoltaic materials if their phase purity and stability can be addressed. Herein, a series of inorganic perovskites is studied, and it is found that the power conversion efficiency of solar cells with compositions CsPbI1.8Br1.2, CsPbI2.0Br1.0, and CsPbI2.2Br0.8 exhibits a high dependence on the initial annealing step that is found to significantly affect the crystallization and texture behavior of the final perovskite film. At its optimized annealing temperature, CsPbI1.8Br1.2 exhibits a pure orthorhombic phase and only one crystal orientation of the (110) plane. Consequently, this allows for the best efficiency of up to 14.6% and the longest operational lifetime, T-S80, of approximate to 300 h, averaged of over six solar cells, during the maximum power point tracking measurement under continuous light illumination and nitrogen atmosphere. This work provides essential progress on the enhancement of photovoltaic performance and stability of CsPbI3 - xBrx perovskite solar cells. KW - cesium lead halides KW - crystal orientation KW - inorganic perovskites KW - ISOS-L-1I protocol KW - phase purity KW - photostability Y1 - 2020 VL - 4 IS - 9 PB - WILEY-VCH CY - Weinheim ER - TY - JOUR A1 - Wang, Qiong A1 - Mosconi, Edoardo A1 - Wolff, Christian Michael A1 - Li, Junming A1 - Neher, Dieter A1 - De Angelis, Filippo A1 - Suranna, Gian Paolo A1 - Grisorio, Roberto A1 - Abate, Antonio T1 - Rationalizing the molecular design of hole-selective contacts to improve charge extraction in Perovskite solar cells JF - dvanced energy materials N2 - Two new hole selective materials (HSMs) based on dangling methylsulfanyl groups connected to the C-9 position of the fluorene core are synthesized and applied in perovskite solar cells. Being structurally similar to a half of Spiro-OMeTAD molecule, these HSMs (referred as FS and DFS) share similar redox potentials but are endowed with slightly higher hole mobility, due to the planarity and large extension of their structure. Competitive power conversion efficiency (up to 18.6%) is achieved by using the new HSMs in suitable perovskite solar cells. Time-resolved photoluminescence decay measurements and electrochemical impedance spectroscopy show more efficient charge extraction at the HSM/perovskite interface with respect to Spiro-OMeTAD, which is reflected in higher photocurrents exhibited by DFS/FS-integrated perovskite solar cells. Density functional theory simulations reveal that the interactions of methylammonium with methylsulfanyl groups in DFS/FS strengthen their electrostatic attraction with the perovskite surface, providing an additional path for hole extraction compared to the sole presence of methoxy groups in Spiro-OMeTAD. Importantly, the low-cost synthesis of FS makes it significantly attractive for the future commercialization of perovskite solar cells. KW - hole extraction KW - hole selective materials KW - perovskite solar cells KW - sulfur KW - triple-cation perovskite Y1 - 2019 U6 - https://doi.org/10.1002/aenm.201900990 SN - 1614-6832 SN - 1614-6840 VL - 9 IS - 28 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Vollbrecht, Joachim A1 - Tokmoldin, Nurlan A1 - Sun, Bowen A1 - Brus, Viktor V. A1 - Shoaee, Safa A1 - Neher, Dieter T1 - Determination of the charge carrier density in organic solar cells BT - a tutorial JF - Journal of applied physics N2 - The increase in the performance of organic solar cells observed over the past few years has reinvigorated the search for a deeper understanding of the loss and extraction processes in this class of device. A detailed knowledge of the density of free charge carriers under different operating conditions and illumination intensities is a prerequisite to quantify the recombination and extraction dynamics. Differential charging techniques are a promising approach to experimentally obtain the charge carrier density under the aforementioned conditions. In particular, the combination of transient photovoltage and photocurrent as well as impedance and capacitance spectroscopy have been successfully used in past studies to determine the charge carrier density of organic solar cells. In this Tutorial, these experimental techniques will be discussed in detail, highlighting fundamental principles, practical considerations, necessary corrections, advantages, drawbacks, and ultimately their limitations. Relevant references introducing more advanced concepts will be provided as well. Therefore, the present Tutorial might act as an introduction and guideline aimed at new prospective users of these techniques as well as a point of reference for more experienced researchers. Published under an exclusive license by AIP Publishing. KW - Electrical properties and parameters KW - Organic semiconductors KW - Solar cells KW - Photoconductivity KW - Capacitance spectroscopy Y1 - 2022 U6 - https://doi.org/10.1063/5.0094955 SN - 0021-8979 SN - 1089-7550 SN - 1520-8850 VL - 131 IS - 22 PB - American Institute of Physics CY - Melville, NY ER - TY - JOUR A1 - Vandewal, Koen A1 - Benduhn, Johannes A1 - Schellhammer, Karl Sebastian A1 - Vangerven, Tim A1 - Rückert, Janna E. A1 - Piersimoni, Fortunato A1 - Scholz, Reinhard A1 - Zeika, Olaf A1 - Fan, Yeli A1 - Barlow, Stephen A1 - Neher, Dieter A1 - Marder, Seth R. A1 - Manca, Jean A1 - Spoltore, Donato A1 - Cuniberti, Gianaurelio A1 - Ortmann, Frank T1 - Absorption Tails of Donor BT - C-60 Blends Provide Insight into Thermally Activated Charge-Transfer Processes and Polaron Relaxation JF - Journal of the American Chemical Society N2 - In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D A complexes occur at photon energies below the optical gaps of both the donors and the C-60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C-60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes. Y1 - 2017 U6 - https://doi.org/10.1021/jacs.6b12857 SN - 0002-7863 VL - 139 IS - 4 SP - 1699 EP - 1704 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Vandewal, Koen A1 - Albrecht, Steve A1 - Hoke, Eric T. A1 - Graham, Kenneth R. A1 - Widmer, Johannes A1 - Douglas, Jessica D. A1 - Schubert, Marcel A1 - Mateker, William R. A1 - Bloking, Jason T. A1 - Burkhard, George F. A1 - Sellinger, Alan A1 - Frechet, Jean M. J. A1 - Amassian, Aram A1 - Riede, Moritz K. A1 - McGehee, Michael D. A1 - Neher, Dieter A1 - Salleo, Alberto T1 - Efficient charge generation by relaxed charge-transfer states at organic interfaces JF - Nature materials N2 - carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold viaweakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer: fullerene, small-molecule:C-60 and polymer: polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. Y1 - 2014 U6 - https://doi.org/10.1038/NMAT3807 SN - 1476-1122 SN - 1476-4660 VL - 13 IS - 1 SP - 63 EP - 68 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Urayama, Kenji A1 - Tsuji, M. A1 - Neher, Dieter T1 - Layer-thinning effects on ferroelectricity and the ferroelectric-to-paraelectric phase transition of vinylidene fluoride-trifluoroethylene copolymer layers Y1 - 2000 ER - TY - JOUR A1 - Urayama, Kenji A1 - Kircher, Oliver A1 - Böhmer, Roland A1 - Neher, Dieter T1 - Investigations of ferroelectric-to-paraelectric phase transition of vinylidenefluoride trifluoroethylene copolymer thin films by electromechanical interferometry Y1 - 1999 ER - TY - JOUR A1 - Ullbrich, Sascha A1 - Benduhn, Johannes A1 - Jia, Xiangkun A1 - Nikolis, Vasileios C. A1 - Tvingstedt, Kristofer A1 - Piersimoni, Fortunato A1 - Roland, Steffen A1 - Liu, Yuan A1 - Wu, Jinhan A1 - Fischer, Axel A1 - Neher, Dieter A1 - Reineke, Sebastian A1 - Spoltore, Donato A1 - Vandewal, Koen T1 - Emissive and charge-generating donor-acceptor interfaces for organic optoelectronics with low voltage losses JF - Nature materials N2 - Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes(1,2). Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range(3,4). In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes(5-7). Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons(8-11). KW - Electronics, photonics and device physics KW - Optoelectronic devices and components KW - Photonic devices KW - Solar energy and photovoltaic technology Y1 - 2019 U6 - https://doi.org/10.1038/s41563-019-0324-5 SN - 1476-1122 SN - 1476-4660 VL - 18 IS - 5 SP - 459 EP - 464 PB - Nature Publ. Group CY - London 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 - JOUR A1 - Tremel, Kim A1 - Fischer, Florian S. U. A1 - Kayunkid, Navaphun A1 - Di Pietro, Riccardo A1 - Tkachov, Roman A1 - Kiriy, Anton A1 - Neher, Dieter A1 - Ludwigs, Sabine A1 - Brinkmann, Martin T1 - Charge transport anisotropy in highly oriented thin films of the acceptor polymer P(NDI2OD-T2) JF - dvanced energy materials N2 - The nanomorphology of the high mobility polymer poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenedicarboximide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} P(NDI2OD-T2) in thin films is explored as a function of different annealing conditions and correlated to optical and electrical properties. While nanofibrils with face-on orientation in form I are obtained directly after spin-coating and annealing below the melt transition temperature, clear evidence of lamellar structures is found after melt-annealing followed by slow cooling to room temperature. Interestingly these structural changes are accompanied by distinct changes in the absorption patterns. Electron diffraction measurements further show clear transitions towards predominant edge-on oriented chains in form II upon melt-annealing. Large-scale alignment with dichroic ratios up to 10 and improved order is achieved by high temperature rubbing and subsequent post-rubbing annealing. These highly oriented morphologies allow anisotropic in-plane charge transport to be probed with top-gate transistors parallel and perpendicular to the polymer chain direction. Mobilities up to 0.1 cm(2) V-1 s(-1) are observed parallel to the polymer chain, which is up to 10 times higher than those perpendicular to the polymer chain. Y1 - 2014 U6 - https://doi.org/10.1002/aenm.201301659 SN - 1614-6832 SN - 1614-6840 VL - 4 IS - 10 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Tokmoldin, Nurlan A1 - Vollbrecht, Joachim A1 - Hosseini, Seyed Mehrdad A1 - Sun, Bowen A1 - Perdigón-Toro, Lorena A1 - Woo, Han Young A1 - Zou, Yingping A1 - Neher, Dieter A1 - Shoaee, Safa T1 - Explaining the fill-factor and photocurrent losses of nonfullerene acceptor-based solar cells by probing the long-range charge carrier diffusion and drift lengths JF - Advanced energy materials N2 - 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. KW - diffusion length KW - drift length KW - figure of merit KW - lifetime‐ mobility product KW - steady‐ state photoconductance Y1 - 2021 U6 - https://doi.org/10.1002/aenm.202100804 SN - 1614-6840 VL - 11 IS - 22 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Tokmoldin, Nurlan A1 - Hosseini, Seyed Mehrdad A1 - Raoufi, Meysam A1 - Phuong, Le Quang A1 - Sandberg, Oskar J. A1 - Guan, Huilan A1 - Zou, Yingping A1 - Neher, Dieter A1 - Shoaee, Safa T1 - Extraordinarily long diffusion length in PM6:Y6 organic solar cells JF - Journal of materials chemistry : A, materials for energy and sustainability N2 - The PM6:Y6 bulk-heterojunction (BHJ) blend system achieves high short-circuit current (J(SC)) values in thick photovoltaic junctions. Here we analyse these solar cells to understand the observed independence of the short-circuit current upon photoactive layer thickness. We employ a range of optoelectronic measurements and analyses, including Mott-Schottky analysis, CELIV, photoinduced absorption spectroscopy, mobility measurements and simulations, to conclude that, the invariant photocurrent for the devices with different active layer thicknesses is associated with the Y6's diffusion length exceeding 300 nm in case of a 300 nm thick cell. This is despite unintentional doping that occurs in PM6 and the associated space-charge effect, which is expected to be even more profound upon photogeneration. This extraordinarily long diffusion length - which is an order of magnitude larger than typical values for organics - dominates transport in the flat-band region of thick junctions. Our work suggests that the performance of the doped PM6:Y6 organic solar cells resembles that of inorganic devices with diffusion transport playing a pivotal role. Ultimately, this is expected to be a key requirement for the fabrication of efficient, high-photocurrent, thick organic solar cells. Y1 - 2020 U6 - https://doi.org/10.1039/d0ta03016c SN - 2050-7488 SN - 2050-7496 VL - 8 IS - 16 SP - 7854 EP - 7860 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Tockhorn, Philipp A1 - Sutter, Johannes A1 - Cruz Bournazou, Alexandros A1 - Wagner, Philipp A1 - Jäger, Klaus A1 - Yoo, Danbi A1 - Lang, Felix A1 - Grischek, Max A1 - Li, Bor A1 - Li, Jinzhao A1 - Shargaieva, Oleksandra A1 - Unger, Eva A1 - Al-Ashouri, Amran A1 - Köhnen, Eike A1 - Stolterfoht, Martin A1 - Neher, Dieter A1 - Schlatmann, Rutger A1 - Rech, Bernd A1 - Stannowski, Bernd A1 - Albrecht, Steve A1 - Becker, Christiane T1 - Nano-optical designs for high-efficiency monolithic perovskite-silicon tandem solar cells JF - Nature nanotechnology N2 - Designing gentle sinusoidal nanotextures enables the realization of high-efficiency perovskite-silicon solar cells
Perovskite-silicon tandem solar cells offer the possibility of overcoming the power conversion efficiency limit of conventional silicon solar cells. Various textured tandem devices have been presented aiming at improved optical performance, but optimizing film growth on surface-textured wafers remains challenging. Here we present perovskite-silicon tandem solar cells with periodic nanotextures that offer various advantages without compromising the material quality of solution-processed perovskite layers. We show a reduction in reflection losses in comparison to planar tandems, with the new devices being less sensitive to deviations from optimum layer thicknesses. The nanotextures also enable a greatly increased fabrication yield from 50% to 95%. Moreover, the open-circuit voltage is improved by 15 mV due to the enhanced optoelectronic properties of the perovskite top cell. Our optically advanced rear reflector with a dielectric buffer layer results in reduced parasitic absorption at near-infrared wavelengths. As a result, we demonstrate a certified power conversion efficiency of 29.80%. Y1 - 2022 U6 - https://doi.org/10.1038/s41565-022-01228-8 SN - 1748-3387 SN - 1748-3395 VL - 17 IS - 11 SP - 1214 EP - 1221 PB - Nature Publishing Group CY - London [u.a.] ER - TY - JOUR A1 - Sun, Bowen A1 - Sandberg, Oskar A1 - Neher, Dieter A1 - Armin, Ardalan A1 - Shoaee, Safa T1 - Wave optics of differential absorption spectroscopy in thick-junction organic solar cells BT - optical artifacts and correction strategies JF - Physical review applied / The American Physical Society N2 - Differential absorption spectroscopy techniques serve as powerful techniques to study the excited species in organic solar cells. However, it has always been challenging to employ these techniques for characterizing thick-junction organic solar cells, especially when a reflective top contact is involved. In this work, we present a detailed and systematic study on how a combination of the presence of the interference effect and a nonuniform charge-distribution profile, severely manipulates experimental spectra and the decay dynamics. Furthermore, we provide a practical methodology to correct these optical artifacts in differential absorption spectroscopies. The results and the proposed correction method generally apply to all kinds of differential absorption spectroscopy techniques and various thin-film systems, such as organics, perovskites, kesterites, and two-dimensional materials. Notably, it is found that the shape of differential absorption spectra can be strongly distorted, starting from 150-nm active-layer thickness; this matches the thickness range of thick-junction organic solar cells and most perovskite solar cells and needs to be carefully considered in experiments. In addition, the decay dynamics of differential absorption spectra is found to be disturbed by optical artifacts under certain conditions. With the help of the proposed correction formalism, differential spectra and the decay dynamics can be characterized on the full device of thin-film solar cells in transmission mode and yield accurate and reliable results to provide design rules for further progress. Y1 - 2022 U6 - https://doi.org/10.1103/PhysRevApplied.17.054016 SN - 2331-7019 VL - 17 IS - 5 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Marquez, Jose A. A1 - Zhang, Shanshan A1 - Hages, Charles J. A1 - Rothhardt, Daniel A1 - Albrecht, Steve A1 - Burn, Paul L. A1 - Meredith, Paul A1 - Unold, Thomas A1 - Neher, Dieter T1 - Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells JF - Nature Energy N2 - The performance of perovskite solar cells is predominantly limited by non-radiative recombination, either through trap-assisted recombination in the absorber layer or via minority carrier recombination at the perovskite/transport layer interfaces. Here, we use transient and absolute photoluminescence imaging to visualize all non-radiative recombination pathways in planar pintype perovskite solar cells with undoped organic charge transport layers. We find significant quasi-Fermi-level splitting losses (135 meV) in the perovskite bulk, whereas interfacial recombination results in an additional free energy loss of 80 meV at each individual interface, which limits the open-circuit voltage (V-oc) of the complete cell to similar to 1.12 V. Inserting ultrathin interlayers between the perovskite and transport layers leads to a substantial reduction of these interfacial losses at both the p and n contacts. Using this knowledge and approach, we demonstrate reproducible dopant-free 1 cm(2) perovskite solar cells surpassing 20% efficiency (19.83% certified) with stabilized power output, a high V-oc (1.17 V) and record fill factor (>81%). KW - Energy science and technology KW - Solar cells Y1 - 2018 U6 - https://doi.org/10.1038/s41560-018-0219-8 SN - 2058-7546 VL - 3 IS - 10 SP - 847 EP - 854 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Wolff, Christian Michael A1 - Amir, Yohai A1 - Paulke, Andreas A1 - Perdigon-Toro, Lorena A1 - Caprioglio, Pietro A1 - Neher, Dieter T1 - Approaching the fill factor Shockley-Queisser limit in stable, dopant-free triple cation perovskite solar cells JF - Energy & Environmental Science N2 - Perovskite solar cells now compete with their inorganic counterparts in terms of power conversion efficiency, not least because of their small open-circuit voltage (V-OC) losses. A key to surpass traditional thin-film solar cells is the fill factor (FF). Therefore, more insights into the physical mechanisms that define the bias dependence of the photocurrent are urgently required. In this work, we studied charge extraction and recombination in efficient triple cation perovskite solar cells with undoped organic electron/hole transport layers (ETL/HTL). Using integral time of flight we identify the transit time through the HTL as the key figure of merit for maximizing the fill factor (FF) and efficiency. Complementarily, intensity dependent photocurrent and V-OC measurements elucidate the role of the HTL on the bias dependence of non-radiative and transport-related loss channels. We show that charge transport losses can be completely avoided under certain conditions, yielding devices with FFs of up to 84%. Optimized cells exhibit power conversion efficiencies of above 20% for 6 mm(2) sized pixels and 18.9% for a device area of 1 cm(2). These are record efficiencies for hybrid perovskite devices with dopant-free transport layers, highlighting the potential of this device technology to avoid charge-transport limitations and to approach the Shockley-Queisser limit. Y1 - 2017 U6 - https://doi.org/10.1039/c7ee00899f SN - 1754-5692 SN - 1754-5706 VL - 10 SP - 1530 EP - 1539 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Le Corre, Vincent M. A1 - Feuerstein, Markus A1 - Caprioglio, Pietro A1 - Koster, Lambert Jan Anton A1 - Neher, Dieter T1 - Voltage-Dependent Photoluminescence and How It Correlates with the Fill Factor and Open-Circuit Voltage in Perovskite Solar Cells JF - Acs energy letters N2 - Optimizing the photoluminescence (PL) yield of a solar cell has long been recognized as a key principle to maximize the power conversion efficiency. While PL measurements are routinely applied to perovskite films and solar cells under open circuit conditions (V-OC), it remains unclear how the emission depends on the applied voltage. Here, we performed PL(V) measurements on perovskite cells with different hole transport layer thicknesses and doping concentrations, resulting in remarkably different fill factors (FFs). The results reveal that PL(V) mirrors the current-voltage (JV) characteristics in the power-generating regime, which highlights an interesting correlation between radiative and nonradiative recombination losses. In particular, high FF devices show a rapid quenching of PL(V) from open-circuit to the maximum power point. We conclude that, while the PL has to be maximized at V-OC at lower biases < V-OC the PL must be rapidly quenched as charges need to be extracted prior to recombination. Y1 - 2019 U6 - https://doi.org/10.1021/acsenergylett.9b02262 SN - 2380-8195 VL - 4 IS - 12 SP - 2887 EP - 2892 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Grischek, Max A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Gutierrez-Partida, Emilio A1 - Peña-Camargo, Francisco A1 - Rothhardt, Daniel A1 - Zhang, Shanshan A1 - Raoufi, Meysam A1 - Wolansky, Jakob A1 - Abdi-Jalebi, Mojtaba A1 - Stranks, Samuel D. A1 - Albrecht, Steve A1 - Kirchartz, Thomas A1 - Neher, Dieter T1 - How to quantify the efficiency potential of neat perovskite films BT - Perovskite semiconductors with an implied efficiency exceeding 28% JF - Advanced Materials N2 - Perovskite photovoltaic (PV) cells have demonstrated power conversion efficiencies (PCE) that are close to those of monocrystalline silicon cells; however, in contrast to silicon PV, perovskites are not limited by Auger recombination under 1-sun illumination. Nevertheless, compared to GaAs and monocrystalline silicon PV, perovskite cells have significantly lower fill factors due to a combination of resistive and non-radiative recombination losses. This necessitates a deeper understanding of the underlying loss mechanisms and in particular the ideality factor of the cell. By measuring the intensity dependence of the external open-circuit voltage and the internal quasi-Fermi level splitting (QFLS), the transport resistance-free efficiency of the complete cell as well as the efficiency potential of any neat perovskite film with or without attached transport layers are quantified. Moreover, intensity-dependent QFLS measurements on different perovskite compositions allows for disentangling of the impact of the interfaces and the perovskite surface on the non-radiative fill factor and open-circuit voltage loss. It is found that potassium-passivated triple cation perovskite films stand out by their exceptionally high implied PCEs > 28%, which could be achieved with ideal transport layers. Finally, strategies are presented to reduce both the ideality factor and transport losses to push the efficiency to the thermodynamic limit. KW - non-radiative interface recombination KW - perovskite solar cells KW - photoluminescence Y1 - 2020 U6 - https://doi.org/10.1002/adma.202000080 SN - 0935-9648 SN - 1521-4095 VL - 32 IS - 17 SP - 1 EP - 10 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Caprioglio, Pietro A1 - Wolff, Christian Michael A1 - Marquez, Jose A. A1 - Nordmann, Joleik A1 - Zhang, Shanshan A1 - Rothhardt, Daniel A1 - Hörmann, Ulrich A1 - Amir, Yohai A1 - Redinger, Alex A1 - Kegelmann, Lukas A1 - Zu, Fengshuo A1 - Albrecht, Steve A1 - Koch, Norbert A1 - Kirchartz, Thomas A1 - Saliba, Michael A1 - Unold, Thomas A1 - Neher, Dieter T1 - The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells JF - Energy & environmental science N2 - Charge transport layers (CTLs) are key components of diffusion controlled perovskite solar cells, however, they can induce additional non-radiative recombination pathways which limit the open circuit voltage (V-OC) of the cell. In order to realize the full thermodynamic potential of the perovskite absorber, both the electron and hole transport layer (ETL/HTL) need to be as selective as possible. By measuring the photoluminescence yield of perovskite/CTL heterojunctions, we quantify the non-radiative interfacial recombination currents in pin- and nip-type cells including high efficiency devices (21.4%). Our study comprises a wide range of commonly used CTLs, including various hole-transporting polymers, spiro-OMeTAD, metal oxides and fullerenes. We find that all studied CTLs limit the V-OC by inducing an additional non-radiative recombination current that is in most cases substantially larger than the loss in the neat perovskite and that the least-selective interface sets the upper limit for the V-OC of the device. Importantly, the V-OC equals the internal quasi-Fermi level splitting (QFLS) in the absorber layer only in high efficiency cells, while in poor performing devices, the V-OC is substantially lower than the QFLS. Using ultraviolet photoelectron spectroscopy and differential charging capacitance experiments we show that this is due to an energy level mis-alignment at the p-interface. The findings are corroborated by rigorous device simulations which outline important considerations to maximize the V-OC. This work highlights that the challenge to suppress non-radiative recombination losses in perovskite cells on their way to the radiative limit lies in proper energy level alignment and in suppression of defect recombination at the interfaces. Y1 - 2019 U6 - https://doi.org/10.1039/c9ee02020a SN - 1754-5692 SN - 1754-5706 VL - 12 IS - 9 SP - 2778 EP - 2788 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Stolterfoht, Martin A1 - Armin, Ardalan A1 - Philippa, Bronson A1 - Neher, Dieter T1 - The Role of Space Charge Effects on the Competition between Recombination and Extraction in Solar Cells with Low-Mobility Photoactive Layers JF - The journal of physical chemistry letters N2 - The competition between charge extraction and nongeminate recombination critically determines the current-voltage characteristics of organic solar cells (OSCs) and their fill factor. As a measure of this competition, several figures of merit (FOMs) have been put forward; however, the impact of space charge effects has been either neglected, or not specifically addressed. Here we revisit recently reported FOMs and discuss the role of space charge effects on the interplay between recombination and extraction. We find that space charge effects are the primary cause for the onset of recombination in so-called non-Langevin systems, which also depends on the slower carrier mobility and recombination coefficient. The conclusions are supported with numerical calculations and experimental results of 25 different donor/acceptor OSCs with different charge transport parameters, active layer thicknesses or composition ratios. The findings represent a conclusive understanding of bimolecular recombination for drift dominated photocurrents and allow one to minimize these losses for given device parameters. Y1 - 2016 U6 - https://doi.org/10.1021/acs.jpclett.6b02106 SN - 1948-7185 VL - 7 SP - 4716 EP - 4721 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Stiller, Burkhard A1 - Karageorgiev, Peter A1 - Geue, Thomas A1 - Morawetz, Knut A1 - Saphiannikova, Marina A1 - Mechau, Norman A1 - Neher, Dieter T1 - Optically induced mass transport studied by scanning near-field optical- and atomic force microscopy N2 - Some functionalised thin organic films show a very unusual property, namely the light induced material transport. This effect enables to generate three-dimensional structures on surfaces of azobenzene containing films only caused by special optical excitation. The physical mechanisms underlying this phenomenon have not yet been fully understood, and in addition, the dimensions of structures created in that way are macroscopic because of the optical techniques and the wavelength of the used light. In order to gain deeper insight into the physical fundamentals of this phenomenon and to open possibilities for applications it is necessary to create and study structures not only in a macroscopic but also in nanometer range. We first report about experiments to generate optically induced nano structures even down to 100 nm size. The optical stimulation was therefore made by a Scanning Near-field Optical Microscope (SNOM). Secondly, physical conditions inside optically generated surface relief gratings were studied by measuring mechanical properties with high lateral resolution via pulse force mode and force distance curves of an AFM Y1 - 2004 SN - 0204-3467 ER - TY - JOUR A1 - Steyrleuthner, Robert A1 - Schubert, Marcel A1 - Jaiser, Frank A1 - Blakesley, James C. A1 - Chen, Zhihua A1 - Facchetti, Antonio A1 - Neher, Dieter T1 - Bulk electron transport and charge injection in a high mobility n-type semiconducting polymer N2 - Bulk electron transport in a high mobility n-type polymer is studied by time-of-flight photocurrent measurements and electron-only devices. Bulk electron mobilities of similar to 5 x 10(-3) cm(2)/Vs are obtained. The analysis of the electron currents suggests the presence of an injection barrier for all conventionally used low workfunction cathodes. Y1 - 2010 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/10008336 U6 - https://doi.org/10.1002/adma.201000232 SN - 0935-9648 ER - TY - JOUR A1 - Steyrleuthner, Robert A1 - Schubert, Marcel A1 - Howard, Ian A1 - Klaumünzer, Bastian A1 - Schilling, Kristian A1 - Chen, Zhihua A1 - Saalfrank, Peter A1 - Laquai, Frederic A1 - Facchetti, Antonio A1 - Neher, Dieter T1 - Aggregation in a high-mobility n-type low-bandgap copolymer with implications on semicrystalline morphology JF - Journal of the American Chemical Society N2 - We explore the photophysics of P(NDI2OD-T2), a high-mobility and air-stable n-type donor/acceptor polymer. Detailed steady-state UV-vis and photoluminescence (PL) measurements on solutions of P(NDI2OD-T2) reveal distinct signatures of aggregation. By performing quantum chemical calculations, we can assign these spectral features to unaggregated and stacked polymer chains. NMR measurements independently confirm the aggregation phenomena of P(NDI2OD-T2) in solution. The detailed analysis of the optical spectra shows that aggregation is a two-step process with different types of aggregates, which we confirm by time-dependent PL measurements. Analytical ultracentrifugation measurements suggest that aggregation takes place within the single polymer chain upon coiling. By transferring these results to thin P(NDI2OD-T2) films, we can conclude that film formation is mainly governed by the chain collapse, leading in general to a high aggregate content of similar to 45%. This process also inhibits the formation of amorphous and disordered P(NDI2OD-T2) films. Y1 - 2012 U6 - https://doi.org/10.1021/ja306844f SN - 0002-7863 VL - 134 IS - 44 SP - 18303 EP - 18317 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Steyrleuthner, Robert A1 - Di Pietro, Riccardo A1 - Collins, Brian A. A1 - Polzer, Frank A1 - Himmelberger, Scott A1 - Schubert, Marcel A1 - Chen, Zhihua A1 - Zhang, Shiming A1 - Salleo, Alberto A1 - Ade, Harald W. A1 - Facchetti, Antonio A1 - Neher, Dieter T1 - The Role of Regioregularity, Crystallinity, and Chain Orientation on Electron Transport in a High-Mobility n-Type Copolymer JF - Journal of the American Chemical Society Y1 - 2014 U6 - https://doi.org/10.1021/ja4118736 SN - 0002-7863 VL - 136 IS - 11 SP - 4245 EP - 4256 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Steyrleuthner, Robert A1 - Bange, Sebastian A1 - Neher, Dieter T1 - Reliable electron-only devices and electron transport in n-type polymers N2 - Current-voltage analysis of single-carrier transport is a popular method for the determination of charge carrier mobilities in organic semiconductors. Although in widespread use for the analysis of hole transport, only a few reports can be found where the method was applied to electron transport. Here, we summarize the experimental difficulties related to the metal electrode leakage currents and nonlinear differential resistance (NDR) effects and explain their origin. We present a modified preparation technique for the metal electrodes and show that it significantly increases the reliability of such measurements. It allows to produce test devices with low leakage currents and without NDR even for thin organic layers. Metal oxides were often discussed as a possible cause of NDR. Our measurements on forcibly oxidized metal electrodes demonstrate that oxide layers are not exclusively responsible for NDR effects. We present electron transport data for two electron-conducting polymers often applied in all-polymer solar cells for a large variety of layer thicknesses and temperatures. The results can be explained by established exponential trapping models. Y1 - 2009 UR - http://jap.aip.org/ U6 - https://doi.org/10.1063/1.3086307 SN - 0021-8979 ER - TY - JOUR A1 - Srikhirin, Toemsak A1 - Laschitsch, Alexander A1 - Neher, Dieter A1 - Johannsmann, Diethelm T1 - Light-induced softening of azobenzene dye-doped polymer films probed with quartz crystal resonators Y1 - 2000 ER - TY - JOUR A1 - Srikhirin, T. A1 - Cimrova, V. A1 - Schiewe, B. A1 - Tzolov, M. A1 - Hagen, R. A1 - Kostromine, S. A1 - Bieringer, Thomas A1 - Neher, Dieter T1 - An Investigation of the photoinduced changes of absoprtion of high-performance photoaddressable Polymers Y1 - 2002 ER - TY - JOUR A1 - Sini, Gjergji A1 - Schubert, Marcel A1 - Risko, Chad A1 - Roland, Steffen A1 - Lee, Olivia P. A1 - Chen, Zhihua A1 - Richter, Thomas V. A1 - Dolfen, Daniel A1 - Coropceanu, Veaceslav A1 - Ludwigs, Sabine A1 - Scherf, Ullrich A1 - Facchetti, Antonio A1 - Frechet, Jean M. J. A1 - Neher, Dieter T1 - On the Molecular Origin of Charge Separation at the Donor-Acceptor Interface JF - Advanced energy materials N2 - Fullerene-based acceptors have dominated organic solar cells for almost two decades. It is only within the last few years that alternative acceptors rival their dominance, introducing much more flexibility in the optoelectronic properties of these material blends. However, a fundamental physical understanding of the processes that drive charge separation at organic heterojunctions is still missing, but urgently needed to direct further material improvements. Here a combined experimental and theoretical approach is used to understand the intimate mechanisms by which molecular structure contributes to exciton dissociation, charge separation, and charge recombination at the donor-acceptor (D-A) interface. Model systems comprised of polythiophene-based donor and rylene diimide-based acceptor polymers are used and a detailed density functional theory (DFT) investigation is performed. The results point to the roles that geometric deformations and direct-contact intermolecular polarization play in establishing a driving force ( energy gradient) for the optoelectronic processes taking place at the interface. A substantial impact for this driving force is found to stem from polymer deformations at the interface, a finding that can clearly lead to new design approaches in the development of the next generation of conjugated polymers and small molecules. KW - donor-acceptor interfaces KW - energy gradients KW - geometrical deformations KW - nonfullerene acceptors KW - organic photovoltaics KW - photocurrent generation KW - polymer solar cells Y1 - 2018 U6 - https://doi.org/10.1002/aenm.201702232 SN - 1614-6832 SN - 1614-6840 VL - 8 IS - 12 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Sianova, D. A1 - Zen, Achmad A1 - Nothofer, Heinz-Georg A1 - Asawapirom, Udom A1 - Scherf, Ullrich A1 - Hagen, R. A1 - Bieringer, Thomas A1 - Kostromine, S. A1 - Neher, Dieter T1 - Photoaddressable alignment layers for fluorescent polymers in polarized electroluminescence devices Y1 - 2002 ER - TY - JOUR A1 - Shoaee, Safa A1 - Armin, Ardalan A1 - Stolterfoht, Martin A1 - Hosseini, Seyed Mehrdad A1 - Kurpiers, Jona A1 - Neher, Dieter T1 - Decoding Charge Recombination through Charge Generation in Organic Solar Cells JF - Solar RRL N2 - The in-depth understanding of charge carrier photogeneration and recombination mechanisms in organic solar cells is still an ongoing effort. In donor:acceptor (bulk) heterojunction organic solar cells, charge photogeneration and recombination are inter-related via the kinetics of charge transfer states-being singlet or triplet states. Although high-charge-photogeneration quantum yields are achieved in many donor:acceptor systems, only very few systems show significantly reduced bimolecular recombination relative to the rate of free carrier encounters, in low-mobility systems. This is a serious limitation for the industrialization of organic solar cells, in particular when aiming at thick active layers. Herein, a meta-analysis of the device performance of numerous bulk heterojunction organic solar cells is presented for which field-dependent photogeneration, charge carrier mobility, and fill factor are determined. Herein, a "spin-related factor" that is dependent on the ratio of back electron transfer of the triplet charge transfer (CT) states to the decay rate of the singlet CT states is introduced. It is shown that this factor links the recombination reduction factor to charge-generation efficiency. As a consequence, it is only in the systems with very efficient charge generation and very fast CT dissociation that free carrier recombination is strongly suppressed, regardless of the spin-related factor. KW - charge generation KW - charge transfers KW - non-Langevin recombination KW - spin-related factors Y1 - 2019 U6 - https://doi.org/10.1002/solr.201900184 SN - 2367-198X VL - 3 IS - 11 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Shivhare, Rishi A1 - Erdmann, Tim A1 - Hoermann, Ulrich A1 - Collado-Fregoso, Elisa A1 - Zeiske, Stefan A1 - Benduhn, Johannes A1 - Ullbrich, Sascha A1 - Huebner, Rene A1 - Hambsch, Mike A1 - Kiriy, Anton A1 - Voit, Brigitte A1 - Neher, Dieter A1 - Vandewal, Koen A1 - Mannsfeld, Stefan C. B. T1 - Alkyl Branching Position in Diketopyrrolopyrrole Polymers BT - Interplay between Fibrillar Morphology and Crystallinity and Their Effect on Photogeneration and Recombination in Bulk-Heterojunction Solar Cells JF - Chemistry of materials : a publication of the American Chemical Society N2 - Diketopyrrolopyrrole (DPP)-based donor acceptor copolymers have gained a significant amount of research interest in the organic electronics community because of their high charge carrier mobilities in organic field-effect transistors (OFETs) and their ability to harvest near-infrared (NIR) photons in solar cells. In this study, we have synthesized four DPP based donor-acceptor copolymers with variations in the donor unit and the branching point of the solubilizing alkyl chains (at the second or sixth carbon position). Grazing incidence wide-angle X-ray scattering (GIWAXS) results suggest that moving the branching point further away from the polymer backbone increases the tendency for aggregation and yields polymer phases with a higher degree of crystallinity (DoC). The polymers were blended with PC70BM and used as active layers in solar cells. A careful analysis of the energetics of the neat polymer and blend films reveals that the charge-transfer state energy (E-CT) of the blend films lies exceptionally close to the singlet energy of the donor (E-D*), indicating near zero electron transfer losses. The difference between the optical gap and open-circuit voltage (V-OC) is therefore determined to be due to rather high nonradiative 418 +/- 13 mV) and unavoidable radiative voltage losses (approximate to 255 +/- 8 mV). Even though the four materials have similar optical gaps, the short-circuit current density (J(SC)) covers a vast span from 7 to 18 mA cm(-2) for the best performing system. Using photoluminescence (PL) quenching and transient charge extraction techniques, we quantify geminate and nongeminate losses and find that fewer excitons reach the donor-acceptor interface in polymers with further away branching points due to larger aggregate sizes. In these material systems, the photogeneration is therefore mainly limited by exciton harvesting efficiency. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b02739 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 19 SP - 6801 EP - 6809 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Shalom, Menny A1 - Inal, Sahika A1 - Neher, Dieter A1 - Antonietti, Markus T1 - SiO2/carbon nitride composite materials: The role of surfaces for enhanced photocatalysis JF - Catalysis today : a serial publication dealing with topical themes in catalysis and related subjects N2 - The effect of SiO2 nanoparticles on carbon nitride (C3N4) photoactivity performance is described. The composite SiO2-C3N4 materials exhibit a higher activity in the photo degradation of RhB dye. A detailed analysis of the chemical and optical properties of the composite C3N4 materials shows that the photo activity increases with higher SiO2 concentration. We found out that the presence of SiO2 nanoparticles strongly affects the fluorescence intensity of the matrix and life time by the creation of new energy states for charge transfer within the C3N4. Furthermore, the use of SiO2 in the synthesis of C3N4 leads to new morphology with higher surface area which results in another, secondary improvement of C3N4 photoactivity. The effect of different surfaces within C3N4 on its chemical and electronic properties is discussed and a tentative mechanism is proposed. The utilization of SiO2 nanoparticles improves both photophysical and chemical properties of C3N4 and opens new possibilities for further enhancement of C3N4 catalytic properties by the formation of composites with many other materials. KW - Carbon nitride KW - SiO2 composite material KW - Photocatalysis KW - RhB degradation Y1 - 2014 U6 - https://doi.org/10.1016/j.cattod.2013.12.013 SN - 0920-5861 SN - 1873-4308 VL - 225 SP - 185 EP - 190 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Shalom, Menny A1 - Inal, Sahika A1 - Fettkenhauer, Christian A1 - Neher, Dieter A1 - Antonietti, Markus T1 - Improving Carbon Nitride Photocatalysis by Supramolecular Preorganization of Monomers JF - Journal of the American Chemical Society N2 - Here we report a new and simple synthetic pathway to form ordered, hollow carbon nitride structures, using a cyanuric acid melamine (CM) complex in ethanol as a starting product. A detailed analysis of the optical and photocatalytic properties shows that optimum hollow carbon nitride structures are formed after 8 h of condensation. For this condensation time, we find a significantly reduced fluorescence intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes. Enhanced charge transfer is seen as well from a drastic increase of the photocatalytic activity in the degradation of rhodamine B dye, which is shown to proceed via photoinduced hole transfer. Moreover, we show that various CM morphologies can be obtained using different solvents, which leads to diverse ordered carbon nitride architectures. In all cases, the CM-C3N4 structures exhibited superior photocatalytic activity compared to the bulk material. The utilization of CM hydrogen-bonded complexes opens new opportunities for the significant improvement of carbon nitride synthesis, structure, and optical properties toward an efficient photoactive material for catalysis. Y1 - 2013 U6 - https://doi.org/10.1021/ja402521s SN - 0002-7863 VL - 135 IS - 19 SP - 7118 EP - 7121 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Shalom, Menny A1 - Guttentag, Miguel A1 - Fettkenhauer, Christian A1 - Inal, Sahika A1 - Neher, Dieter A1 - Llobet, Antoni A1 - Antonietti, Markus T1 - In situ formation of heterojunctions in modified graphitic carbon nitride: synthesis and noble metal free photocatalysis JF - Chemistry of materials : a publication of the American Chemical Society N2 - Herein, we report the facile synthesis of an efficient roll-like carbon nitride (C3N4) photocatalyst for hydrogen production using a supramolecular complex composed of cyanuric acid, melamine, and barbituric acid as the starting monomers. Optical and photocatalytic investigations show, along with the known red shift of absorption into the visible region, that the insertion of barbituric acid results in the in situ formation of in-plane heterojuctions, which enhance the charge separation process under illumination. Moreover, platinum as the standard cocatalyst in photocatalysis could be successfully replaced with first row transition metal salts and complexes under retention of 50% of the catalytic activity. Their mode of deposition and interaction with the semiconductor was studied in detail. Utilization of the supramolecular approach opens new opportunities to manipulate the charge transfer process within carbon nitride with respect to the design of a more efficient carbon nitride photocatalyst with controlled morphology and optical properties. Y1 - 2014 U6 - https://doi.org/10.1021/cm503258z SN - 0897-4756 SN - 1520-5002 VL - 26 IS - 19 SP - 5812 EP - 5818 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schwarze, Martin A1 - Schellhammer, Karl Sebastian A1 - Ortstein, Katrin A1 - Benduhn, Johannes A1 - Gaul, Christopher A1 - Hinderhofer, Alexander A1 - Toro, Lorena Perdigon A1 - Scholz, Reinhard A1 - Kublitski, Jonas A1 - Roland, Steffen A1 - Lau, Matthias A1 - Poelking, Carl A1 - Andrienko, Denis A1 - Cuniberti, Gianaurelio A1 - Schreiber, Frank A1 - Neher, Dieter A1 - Vandewal, Koen A1 - Ortmann, Frank A1 - Leo, Karl T1 - Impact of molecular quadrupole moments on the energy levels at organic heterojunctions JF - Nature Communications N2 - 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. Y1 - 2019 U6 - https://doi.org/10.1038/s41467-019-10435-2 SN - 2041-1723 VL - 10 PB - Nature Publ. Group CY - London ER - TY - JOUR A1 - Schulze, Patricia S. C. A1 - Bett, Alexander J. A1 - Bivour, Martin A1 - Caprioglio, Pietro A1 - Gerspacher, Fabian M. A1 - Kabaklı, Özde Ş. A1 - Richter, Armin A1 - Stolterfoht, Martin A1 - Zhang, Qinxin A1 - Neher, Dieter A1 - Hermle, Martin A1 - Hillebrecht, Harald A1 - Glunz, Stefan W. A1 - Goldschmidt, Jan Christoph T1 - 25.1% high-efficiency monolithic perovskite silicon tandem solar cell with a high bandgap perovskite absorber JF - Solar RRL N2 - Monolithic perovskite silicon tandem solar cells can overcome the theoretical efficiency limit of silicon solar cells. This requires an optimum bandgap, high quantum efficiency, and high stability of the perovskite. Herein, a silicon heterojunction bottom cell is combined with a perovskite top cell, with an optimum bandgap of 1.68 eV in planar p-i-n tandem configuration. A methylammonium-free FA(0.75)Cs(0.25)Pb(I0.8Br0.2)(3) perovskite with high Cs content is investigated for improved stability. A 10% molarity increase to 1.1 m of the perovskite precursor solution results in approximate to 75 nm thicker absorber layers and 0.7 mA cm(-2) higher short-circuit current density. With the optimized absorber, tandem devices reach a high fill factor of 80% and up to 25.1% certified efficiency. The unencapsulated tandem device shows an efficiency improvement of 2.3% (absolute) over 5 months, showing the robustness of the absorber against degradation. Moreover, a photoluminescence quantum yield analysis reveals that with adapted charge transport materials and surface passivation, along with improved antireflection measures, the high bandgap perovskite absorber has the potential for 30% tandem efficiency in the near future. KW - heterojunction silicon solar cells KW - interfaces KW - perovskite solar cells KW - tandem solar cells KW - thin films Y1 - 2020 VL - 4 IS - 7 PB - John Wiley & Sons, Inc. CY - New Jersey ER - TY - JOUR A1 - Schubert, Marcel A1 - Yin, Chunhong A1 - Castellani, Mauro A1 - Bange, Sebastian A1 - Tam, Teck Lip A1 - Sellinger, Alan A1 - Hoerhold, Hans-Heinrich A1 - Kietzke, Thomas A1 - Neher, Dieter T1 - Heterojunction topology versus fill factor correlations in novel hybrid small-molecular/polymeric solar cells N2 - The authors present organic photovoltaic (OPV) devices comprising a small molecule electron acceptor based on 2- vinyl-4,5-dicyanoimidazole (Vinazene (TM)) and a soluble poly(p-phenylenevinylene) derivative as the electron donor. A strong dependence of the fill factor (FF) and the external quantum efficiency [incident photons converted to electrons (IPCE)] on the heterojunction topology is observed. As-prepared blends provided relatively low FF and IPCE values of 26% and 4.5%, respectively, which are attributed to significant recombination of geminate pairs and free carriers in a highly intermixed blend morphology. Going to an all-solution processed bilayer device, the FF and IPCE dramatically increased to 43% and 27%, respectively. The FF increases further to 57% in devices comprising thermally deposited Vinazene layers where there is virtually no interpenetration at the donor/acceptor interface. This very high FF is comparable to values reported for OPV using fullerenes as the electron acceptor. Furthermore, the rather low electron affinity of Vinazene compound near 3.5 eV enabled a technologically important open circuit voltage (V-oc) of 1.0 V. Y1 - 2009 UR - http://jcp.aip.org/ U6 - https://doi.org/10.1063/1.3077007 SN - 0021-9606 ER - TY - JOUR A1 - Schubert, Marcel A1 - Steyrleuthner, Robert A1 - Bange, Sebastian A1 - Sellinger, Alan A1 - Neher, Dieter T1 - Charge transport and recombination in bulk heterojunction solar cells containing a dicyanoimidazole-based molecular acceptor N2 - Carrier transport and recombination have been studied in single component layers and blends of the soluble PPV- derivative poly[2,5-dimethoxy-1,4-phenylenevinylene-2-methoxy-5-(2-ethyl-hexyloxy)- 1,4-phenylenevinylene] (M3EH-PPV) and the small molecule acceptor 4,7-bis(2-(1-hexyl-4,5-dicyanoimidazole-2-yl)vinyl) benzo[c][1,2,5]-thiadiazole (HV-BT). Measurements on single carrier devices show significantly smaller electron mobility in the blend compared to the pure HV- BT layer, which is suggestive of the formation of isolated clusters of the acceptor in a continuous polymer matrix. The significant change in fill factor (FF) with increasing illumination intensity is consistently explained by a model taking into account bimolecular recombination and space charge effects. The decay of the carrier density after photoexcitation has been studied by performing photo-CELIV measurements on pure and blend layers. It is found that the decay at long delay times follows a power-law dependence, which is, however, not consistent with a Langevin-type bimolecular recombination of free charges. A good description of the data is obtained by assuming trimolecular recombination to govern the charge carrier dynamics in these systems. Y1 - 2009 UR - http://www3.interscience.wiley.com/cgi-bin/jhome/40000761 U6 - https://doi.org/10.1002/pssa.200925312 SN - 1862-6300 ER - TY - JOUR A1 - Schubert, Marcel A1 - Preis, Eduard A1 - Blakesley, James C. A1 - Pingel, Patrick A1 - Scherf, Ullrich A1 - Neher, Dieter T1 - Mobility relaxation and electron trapping in a donor/acceptor copolymer JF - Physical review : B, Condensed matter and materials physics N2 - To address the nature of charge transport and the origin of severe (intrinsic) trapping in electron-transporting polymers, transient and steady-state charge transport measurements have been conducted on the prototype donor/acceptor copolymer poly[2,7-(9,9-dialkyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (PFTBTT). A charge-generation layer technique is used to selectively address transport of the desired charge carrier type, to perform time-of-flight measurements on samples with < 200 nm thickness, and to combine the time-of-flight and the photocharge extraction by linearly increasing voltage (photo-CELIV) techniques to investigate charge carrier dynamics over a wide time range. Significant trapping of free electrons is observed in the bulk of dioctyl-substituted PFTBTT (alt-PF8TBTT), introducing a strong relaxation of the charge carrier mobility with time. We used Monte-Carlo simulation to simulate the measured transient data and found that all measurements can be modeled with a single parameter set, with the charge transport behavior determined by multiple trapping and detrapping of electrons in an exponential trap distribution. The influence of the concomitant mobility relaxation on the transient photocurrent characteristics in photo-CELIV experiments is discussed and shown to explain subtle features that were seen in former publications but were not yet assigned to electron trapping. Comparable studies on PFTBTT copolymers with chemical modifications of the side chains and backbone suggest that the observed electron trapping is not caused by a distinct chemical species but rather is related to interchain interactions. Y1 - 2013 U6 - https://doi.org/10.1103/PhysRevB.87.024203 SN - 1098-0121 VL - 87 IS - 2 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Schubert, Marcel A1 - Frisch, Johannes A1 - Allard, Sybille A1 - Preis, Eduard A1 - Scherf, Ullrich A1 - Koch, Norbert A1 - Neher, Dieter T1 - Tuning side chain and main chain order in a prototypical donor-acceptor copolymer BT - implications for optical, electronic, and photovoltaic characteristics JF - Elementary Processes in Organic Photovoltaics N2 - The recent development of donor–acceptor copolymers has led to an enormous improvement in the performance of organic solar cells and organic field-effect transistors. Here we describe the synthesis, detailed characterisation, and application of a series of structurally modified copolymers to investigate fundamental structure–property relationships in this class of conjugated polymers. The interplay between chemical structure and optoelectronic properties is investigated. These are further correlated to the charge transport and solar cell performance, which allows us to link their chemical structure to the observed physical properties. KW - Aggregate states KW - All-polymer heterojunctions KW - Alternating copolymers KW - Ambipolar charge transport KW - Ambipolar materials KW - Backbone modifications KW - Bilayer solar cells KW - Charge separation KW - Conformational disorder KW - Crystalline phases KW - Donor-acceptor copolymers KW - Electron traps KW - Energetic disorder KW - Energy-level alignment KW - Fermi-level alignment KW - Fermi-level pinning KW - Interface dipole KW - Interlayer KW - Intrachain order KW - Intragap states KW - Microscopic morphology KW - Mobility imbalance KW - Mobility relaxation KW - Monte Carlo simulation KW - Multiple trapping model KW - Nonradiative recombination KW - OFET KW - Open-circuit voltage KW - Optoelectronic properties KW - Partially alternating copolymers KW - Photo-CELIV KW - Photocurrent KW - Photovoltaic gap KW - Polymer intermixing KW - Recombination losses KW - Spectral diffusion KW - Statistical copolymers KW - Stille-type cross-coupling KW - Structure-property relationships KW - Time-dependent mobility KW - Time-of-flight (TOF) KW - Transient photocurrent KW - Ultraviolet photoelectron spectroscopy KW - Vacuum-level alignment KW - X-ray photoelectron spectroscopy Y1 - 2016 SN - 978-3-319-28338-8 SN - 978-3-319-28336-4 U6 - https://doi.org/10.1007/978-3-319-28338-8_10 SN - 0065-3195 VL - 272 SP - 243 EP - 265 PB - Springer CY - Berlin 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 - Schubert, Marcel A1 - Collins, Brian A. A1 - Mangold, Hannah A1 - Howard, Ian A. A1 - Schindler, Wolfram A1 - Vandewal, Koen A1 - Roland, Steffen A1 - Behrends, Jan A1 - Kraffert, Felix A1 - Steyrleuthner, Robert A1 - Chen, Zhihua A1 - Fostiropoulos, Konstantinos A1 - Bittl, Robert A1 - Salleo, Alberto A1 - Facchetti, Antonio A1 - Laquai, Frederic A1 - Ade, Harald W. A1 - Neher, Dieter T1 - Correlated donor/acceptor crystal orientation controls photocurrent generation in all-polymer solar cells JF - Advanced functional materials N2 - New polymers with high electron mobilities have spurred research in organic solar cells using polymeric rather than fullerene acceptors due to their potential of increased diversity, stability, and scalability. However, all-polymer solar cells have struggled to keep up with the steadily increasing power conversion efficiency of polymer: fullerene cells. The lack of knowledge about the dominant recombination process as well as the missing concluding picture on the role of the semi-crystalline microstructure of conjugated polymers in the free charge carrier generation process impede a systematic optimization of all-polymer solar cells. These issues are examined by combining structural and photo-physical characterization on a series of poly(3-hexylthiophene) (donor) and P(NDI2OD-T2) (acceptor) blend devices. These experiments reveal that geminate recombination is the major loss channel for photo-excited charge carriers. Advanced X-ray and electron-based studies reveal the effect of chloronaphthalene co-solvent in reducing domain size, altering domain purity, and reorienting the acceptor polymer crystals to be coincident with those of the donor. This reorientation correlates well with the increased photocurrent from these devices. Thus, effi cient split-up of geminate pairs at polymer/polymer interfaces may necessitate correlated donor/acceptor crystal orientation, which represents an additional requirement compared to the isotropic fullerene acceptors. Y1 - 2014 U6 - https://doi.org/10.1002/adfm.201304216 SN - 1616-301X SN - 1616-3028 VL - 24 IS - 26 SP - 4068 EP - 4081 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Schattauer, Sylvia A1 - Reinhold, Beate A1 - Albrecht, Steve A1 - Fahrenson, Christoph A1 - Schubert, Marcel A1 - Janietz, Silvia A1 - Neher, Dieter T1 - Influence of sintering on the structural and electronic properties of TiO2 nanoporous layers prepared via a non-sol-gel approach JF - Colloid and polymer science : official journal of the Kolloid-Gesellschaft N2 - In this work, a nonaqueous method is used to fabricate thin TiO2 layers. In contrast to the common aqueous sol-gel approach, our method yields layers of anatase nanocrystallites already at low temperature. Raman spectroscopy, electron microscopy and charge extraction by linearly increasing voltage are employed to study the effect of sintering temperature on the structural and electronic properties of the nanocrystalline TiO2 layer. Raising the sintering temperature from 120 to 600 A degrees C is found to alter the chemical composition, the layer's porosity and its surface but not the crystal phase. The room temperature mobility increases from 2 x 10(-6) to 3 x 10(-5) cm(2)/Vs when the sinter temperature is increased from 400 to 600 A degrees C, which is explained by a better interparticle connectivity. Solar cells comprising such nanoporous TiO2 layers and a soluble derivative of cyclohexylamino-poly(p-phenylene vinylene) were fabricated and studied with regard to their structural and photovoltaic properties. We found only weak polymer infiltration into the oxide layer for sintering temperatures up to 550 A degrees C, while the polymer penetrated deeply into titania layers that were sintered at 600 A degrees C. Best photovoltaic performance was reached with a nanoporous TiO2 film sintered at 550 A degrees C, which yielded a power conversion efficiency of 0.5 %. Noticeably, samples with the TiO2 layer dried at 120 A degrees C displayed short-circuit currents and open circuit voltages only about 15-20 % lower than for the most efficient devices, meaning that our nonaqueous route yields titania layers with reasonable transport properties even at low sintering temperatures. KW - Nonaqueous sol-gel KW - Thin nanocrystalline TiO2 layer KW - Solar cells KW - Effect of sintering KW - Linearly increasing voltage (CELIV) KW - Polymer infiltration KW - Transport properties titania KW - Transient fluorescence Y1 - 2012 U6 - https://doi.org/10.1007/s00396-012-2708-9 SN - 0303-402X VL - 290 IS - 18 SP - 1843 EP - 1854 PB - Springer CY - New York ER - TY - JOUR A1 - Scharsich, Christina A1 - Lohwasser, Ruth H. A1 - Sommer, Michael A1 - Asawapirom, Udom A1 - Scherf, Ullrich A1 - Thelakkat, Mukundan A1 - Neher, Dieter A1 - Koehler, Anna T1 - Control of aggregate formation in poly(3-hexylthiophene) by solvent, molecular weight, and synthetic method JF - Journal of polymer science : B, Polymer physics N2 - Aggregate formation in poly(3-hexylthiophene) depends on molecular weight, solvent, and synthetic method. The interplay of these parameters thus largely controls device performance. In order to obtain a quantitative understanding on how these factors control the resulting electronic properties of P3HT, we measured absorption in solution and in thin films as well as the resulting field effect mobility in transistors. By a detailed analysis of the absorption spectra, we deduce the fraction of aggregates formed, the excitonic coupling within the aggregates, and the conjugation length within the aggregates, all as a function of solvent quality for molecular weights from 5 to 19 kDa. From this, we infer in which structure the aggregated chains pack. Although the 5 kDa samples form straight chains, the 11 and 19 kDa chains are kinked or folded, with conjugation lengths that increase as the solvent quality reduces. There is a maximum fraction of aggregated chains (about 55 +/- 5%) that can be obtained, even for poor solvent quality. We show that inducing aggregation in solution leads to control of aggregate properties in thin films. As expected, the field-effect mobility correlates with the propensity to aggregation. Correspondingly, we find that a well-defined synthetic approach, tailored to give a narrow molecular weight distribution, is needed to obtain high field effect mobilities of up to 0.01 cm2/Vs for low molecular weight samples (=11 kDa), while the influence of synthetic method is negligible for samples of higher molecular weight, if low molecular weight fractions are removed by extraction. KW - conformational analysis KW - conjugated polymers KW - crystallization KW - films KW - interaction parameter KW - molecular weight distribution KW - molar mass distribution KW - nucleation KW - photophysics KW - structure KW - UV-vis spectroscopy Y1 - 2012 U6 - https://doi.org/10.1002/polb.23022 SN - 0887-6266 VL - 50 IS - 6 SP - 442 EP - 453 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Saphiannikova, Marina A1 - Neher, Dieter T1 - Thermodynamic theory of light-induced material transport in amorphous azobenzene polymer films N2 - It was discovered 10 years ago that the exposure of an initially flat layer of an azobenzene-containing polymer to an inhomogeneous light pattern leads to the formation of surface relief structures, accompanied by a mass transport over several micrometers. However, the driving force of this process is still unclear. We propose a new thermodynamic approach that explains a number of experimental findings including the light-induced deformation of free-standing films and the formation of surface relief gratings for main inscription geometries. Our basic assumption is that under homogeneous illumination, an initially isotropic sample should stretch itself along the polarization direction to compensate the entropy decrease produced by the photoinduced reorientation of azobenzene chromophores. The magnitude of the elastic stress, estimated by taking the derivative of the free energy over the sample deformation, is shown to be sufficient to induce plastic deformation of the polymer film. Orientational distributions of chromophores predicted by our model are compared with those deduced from Raman intensity measurements Y1 - 2005 SN - 1520-6106 ER - TY - JOUR A1 - Sandberg, Oskar J. A1 - Kurpiers, Jona A1 - Stolterfoht, Martin A1 - Neher, Dieter A1 - Meredith, Paul A1 - Shoaee, Safa A1 - Armin, Ardalan T1 - On the question of the need for a built-in potential in Perovskite solar cells JF - Advanced materials interfaces N2 - Perovskite semiconductors as the active materials in efficient solar cells exhibit free carrier diffusion lengths on the order of microns at low illumination fluxes and many hundreds of nanometers under 1 sun conditions. These lengthscales are significantly larger than typical junction thicknesses, and thus the carrier transport and charge collection should be expected to be diffusion controlled. A consensus along these lines is emerging in the field. However, the question as to whether the built-in potential plays any role is still of matter of some conjecture. This important question using phase-sensitive photocurrent measurements and theoretical device simulations based upon the drift-diffusion framework is addressed. In particular, the role of the built-in electric field and charge-selective transport layers in state-of-the-art p-i-n perovskite solar cells comparing experimental findings and simulation predictions is probed. It is found that while charge collection in the junction does not require a drift field per se, a built-in potential is still needed to avoid the formation of reverse electric fields inside the active layer, and to ensure efficient extraction through the charge transport layers. KW - built-in potential KW - charge collection KW - charge transport layers KW - perovskite solar cells Y1 - 2020 U6 - https://doi.org/10.1002/admi.202000041 SN - 2196-7350 VL - 7 IS - 10 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Samson, Stephanie A1 - Rech, Jeromy A1 - Perdigon-Toro, Lorena A1 - Peng, Zhengxing A1 - Shoaee, Safa A1 - Ade, Harald A1 - Neher, Dieter A1 - Stolterfoht, Martin A1 - You, Wei T1 - Organic solar cells with large insensitivity to donor polymer molar mass across all acceptor classes JF - ACS applied polymer materials N2 - Donor polymer number-average molar mass (M-n) has long been known to influence organic photovoltaic (OPV) performance via changes in both the polymer properties and the resulting bulk heterojunction morphology. The exact nature of these M-n effects varies from system to system, although there is generally some intermediate M-n that results in optimal performance. Interestingly, our earlier work with the difluorobenzotriazole (FTAZ)-based donor polymer, paired with either N2200 (polymer acceptor) or PC61BM (fullerene acceptor), PcBm demonstrated <10% variation in power conversion efficiency and a consistent morphology over a large span of M-n (30 kg/mol to over 100 kg/mol). Would such insensitivity to polymer M-n still hold true when prevailing small molecular acceptors were used with FTAZ? To answer this question, we explored the impact of FTAZ on OPVs with ITIC, a high-performance small-molecule fused-ring electron acceptor (FREA). By probing the photovoltaic characteristics of the resulting OPVs, we show that a similar FTAZ mn insensitivity is also found in the FTAZ:ITIC system. This study highlights a single-donor polymer which, when paired with an archetypal fullerene, polymer, and FREA, results in systems that are largely insensitive to donor M. Our results may have implications in polymer batch-to-batch reproducibility, in particular, relaxing the need for tight M-n control during synthesis. KW - polymer solar cells KW - conjugated polymers KW - fullerenes KW - fluorination KW - molecular weight KW - non-fullerene acceptors KW - power conversion efficiency Y1 - 2020 U6 - https://doi.org/10.1021/acsapm.0c01041 SN - 2637-6105 VL - 2 IS - 11 SP - 5300 EP - 5308 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Saliba, Michael A1 - Correa-Baena, Juan-Pablo A1 - Wolff, Christian M. A1 - Stolterfoht, Martin A1 - Phung, Thi Thuy Nga A1 - Albrecht, Steve A1 - Neher, Dieter A1 - Abate, Antonio T1 - How to Make over 20% Efficient Perovskite Solar Cells in Regular (n-i-p) and Inverted (p-i-n) Architectures JF - Chemistry of materials : a publication of the American Chemical Society N2 - Perovskite solar cells (PSCs) are currently one of the most promising photovoltaic technologies for highly efficient and cost-effective solar energy production. In only a few years, an unprecedented progression of preparation procedures and material compositions delivered lab-scale devices that have now reached record power conversion efficiencies (PCEs) higher than 20%, competing with most established solar cell materials such as silicon, CIGS, and CdTe. However, despite a large number of researchers currently involved in this topic, only a few groups in the world can reproduce >20% efficiencies on a regular n-i-p architecture. In this work, we present detailed protocols for preparing PSCs in regular (n-i-p) and inverted (p-i-n) architectures with >= 20% PCE. We aim to provide a comprehensive, reproducible description of our device fabrication , protocols. We encourage the practice of reporting detailed and transparent protocols that can be more easily reproduced by other laboratories. A better reporting standard may, in turn, accelerate the development of perovskite solar cells and related research fields. Y1 - 2018 U6 - https://doi.org/10.1021/acs.chemmater.8b00136 SN - 0897-4756 SN - 1520-5002 VL - 30 IS - 13 SP - 4193 EP - 4201 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Salert, Beatrice Ch. D. A1 - Krueger, Hartmut A1 - Bagnich, Sergey A. A1 - Unger, Thomas A1 - Jaiser, Frank A1 - Al-Sa'di, Mahmoud A1 - Neher, Dieter A1 - Hayer, Anna A1 - Eberle, Thomas T1 - New polymer matrix system for phosphorescent organic light-emitting diodes and the role of the small molecular co-host JF - Journal of polymer science : A, Polymer chemistry N2 - 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. KW - charge transport KW - conducting polymer KW - degradation KW - host-guest systems KW - light-emitting diodes KW - random copolymer KW - synthesis KW - UV-vis spectroscopy Y1 - 2013 U6 - https://doi.org/10.1002/pola.26409 SN - 0887-624X VL - 51 IS - 3 SP - 601 EP - 613 PB - Wiley-Blackwell CY - Hoboken ER - TY - JOUR A1 - Sainova, Dessislava A1 - Miteva, T. A1 - Nothofer, Heinz-Georg A1 - Scherf, Ullrich A1 - Fujikawa, H. A1 - Glowacki, Ireneusz A1 - Ulanski, J. A1 - Neher, Dieter T1 - Control of color and efficiency of light-emitting diodes based on polyfluorenes blended with hole-transporting molecules Y1 - 2000 ER - TY - JOUR A1 - Sainova, Dessislava A1 - Fujikawa, H. A1 - Scherf, Ullrich A1 - Neher, Dieter T1 - The effect of hole traps on the performance of single layer polymer light emitting diodes Y1 - 1999 ER - TY - JOUR A1 - Roland, Steffen A1 - Yan, Liang A1 - Zhang, Qianqian A1 - Jiao, Xuechen A1 - Hunt, Adrian A1 - Ghasemi, Masoud A1 - Ade, Harald A1 - You, Wei A1 - Neher, Dieter T1 - Charge Generation and Mobility-Limited Performance of Bulk Heterojunction Solar Cells with a Higher Adduct Fullerene JF - The journal of physical chemistry : C, Nanomaterials and interfaces N2 - Alternative electron acceptors are being actively explored in order to advance the development of bulk-heterojunction (BHJ) organic solar cells (OSCs). The indene-C-60 bisadduct (ICBA) has been regarded as a promising candidate, as it provides high open-circuit voltage in BHJ solar cells; however, the photovoltaic performance of such ICBA-based devices is often inferior when compared to cells with the omnipresent PCBM electron acceptor. Here, by pairing the high performance polymer (FTAZ) as the donor with either PCBM or ICBA as the acceptor, we explore the physical mechanism behind the reduced performance of the ICBA-based device. Time delayed collection field (TDCF) experiments reveal reduced, yet field-independent free charge generation in the FTAZ:ICBA system, explaining the overall lower photocurrent in its cells. Through the analysis of the photoluminescence, photogeneration, and electroluminescence, we find that the lower generation efficiency is neither caused by inefficient exciton splitting, nor do we find evidence for significant energy back-transfer from the CT state to singlet excitons. In fact, the increase in open circuit voltage when replacing PCBM by ICBA is entirely caused by the increase in the CT energy, related to the shift in the LUMO energy, while changes in the radiative and nonradiative recombination losses are nearly absent. On the other hand, space charge limited current (SCLC) and bias-assisted charge extraction (BACE) measurements consistently reveal a severely lower electron mobilitiy in the FTAZ:ICBA blend. Studies of the blends with resonant soft X-ray scattering (R-SoXS), grazing incident wide-angle X-ray scattering (GIWAXS), and scanning transmission X-ray microscopy (STXM) reveal very little differences in the mesoscopic morphology but significantly less nanoscale molecular ordering of the fullerene domains in the ICBA based blends, which we propose as the main cause for the lower generation efficiency and smaller electron mobility. Calculations of the JV curves with an analytical model, using measured values, show good agreement with the experimentally determined JV characteristics, proving that these devices suffer from slow carrier extraction, resulting in significant bimolecular recombination losses. Therefore, this study highlights the importance of high charge carrier mobility for newly synthesized acceptor materials, in addition to having suitable energy levels. Y1 - 2017 U6 - https://doi.org/10.1021/acs.jpcc.7b02288 SN - 1932-7447 VL - 121 SP - 10305 EP - 10316 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Roland, Steffen A1 - Schubert, Marcel A1 - Collins, Brian A. A1 - Kurpiers, Jona A1 - Chen, Zhihua A1 - Facchetti, Antonio A1 - Ade, Harald W. A1 - Neher, Dieter T1 - Fullerene-free polymer solar cells with highly reduced bimolecular recombination and field-independent charge carrier generation JF - The journal of physical chemistry letters N2 - Photogeneration, recombination, and transport of free charge carriers in all-polymer bulk heterojunction solar cells incorporating poly(3-hexylthiophene) (P3HT) as donor and poly([N,N'-bis(2-octyldodecyl)-naphthelene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)) (P(NDI2OD-T2)) as acceptor polymer have been investigated by the use of time delayed collection field (TDCF) and time-of-flight (TOF) measurements. Depending on the preparation procedure used to dry the active layers, these solar cells comprise high fill factors (FFs) of up to 67%. A strongly reduced bimolecular recombination (BMR), as well as a field-independent free charge carrier generation are observed, features that are common to high performance fullerene-based solar cells. Resonant soft X-ray measurements (R-SoXS) and photoluminescence quenching experiments (PQE) reveal that the BMR is related to domain purity. Our results elucidate the similarities of this polymeric acceptor with the superior recombination properties of fullerene acceptors. Y1 - 2014 U6 - https://doi.org/10.1021/jz501506z SN - 1948-7185 VL - 5 IS - 16 SP - 2815 EP - 2822 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Roland, Steffen A1 - Neubert, Sebastian A1 - Albrecht, Steve A1 - Stannowski, Bernd A1 - Seger, Mark A1 - Facchetti, Antonio A1 - Schlatmann, Rutger A1 - Rech, Bernd A1 - Neher, Dieter T1 - Hybrid Organic/Inorganic Thin-Film Multijunction Solar Cells Exceeding 11% Power Conversion Efficiency JF - Advanced materials N2 - Hybrid multijunction solar cells comprising hydrogenated amorphous silicon and an organic bulk heterojunction are presented, reaching 11.7% power conversion efficiency. The benefits of merging inorganic and organic subcells are pointed out, the optimization of the cells, including optical modeling predictions and tuning of the recombination contact are described, and an outlook of this technique is given. Y1 - 2015 U6 - https://doi.org/10.1002/adma.201404698 SN - 0935-9648 SN - 1521-4095 VL - 27 IS - 7 SP - 1262 EP - 1267 PB - Wiley-VCH CY - Weinheim 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 - Rivnay, Jonathan A1 - Steyrleuthner, Robert A1 - Jimison, Leslie H. A1 - Casadei, Alberto A1 - Chen, Zhihua A1 - Toney, Michael F. A1 - Facchetti, Antonio A1 - Neher, Dieter A1 - Salleo, Alberto T1 - Drastic control of texture in a high performance n-Type polymeric semiconductor and implications for charge transport JF - Macromolecules : a publication of the American Chemical Society N2 - Control of crystallographic texture from mostly face-on to edge-on is observed for the film morphology of the n-type semicrystalline polymer [N,N-9-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diy1]alt-5,59-(2,29-bithiophene)}, P(NDI2OD-T2), when annealing the film to the polymer melting point followed by slow cooling to ambient temperature. A variety of X-ray diffraction analyses, including pole figure construction and Fourier transform peak shape deconvolution, are employed to quantify the texture change, relative degree of crystallinity and lattice order. We find that annealing the polymer film to the melt leads to a shift from 77.5% face-on to 94.6% edge-on lamellar texture as well as to a 2-fold increase in crystallinity and a 40% decrease in intracrystallite cumulative disorder. The texture change results in a significant drop in the electron-only diode current density through the film thickness upon melt annealing while little change is observed in the in-plane transport of bottom gated thin film transistors. This suggests that the texture change is prevalent in the film interior and that either the (bottom) surface structure is different from the interior structure or the intracrystalline order and texture play a secondary role in transistor transport for this material. Y1 - 2011 U6 - https://doi.org/10.1021/ma200864s SN - 0024-9297 VL - 44 IS - 13 SP - 5246 EP - 5255 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Rengel, Heiko A1 - Gattinger, P. A1 - Silverova, R. A1 - Neher, Dieter T1 - Conductivity measurements of electrochemically oxidized Langmuir-Blodgett films of phthalocyaninato- polysiloxanes Y1 - 1999 ER - TY - JOUR A1 - Rengel, Heiko A1 - Altmann, Markus A1 - Neher, Dieter A1 - Harrison, Craig B. A1 - Myrick, Michael L. A1 - Bunz, Uwe H. F. T1 - Assignment of the optical transitions in 1,3- diethynylcyclobutadiene (cyclopentadienyl)cobalt oligomers Y1 - 1999 ER - TY - JOUR A1 - Ran, Niva A. A1 - Roland, Steffen A1 - Love, John A. A1 - Savikhin, Victoria A1 - Takacs, Christopher J. A1 - Fu, Yao-Tsung A1 - Li, Hong A1 - Coropceanu, Veaceslav A1 - Liu, Xiaofeng A1 - Bredas, Jean-Luc A1 - Bazan, Guillermo C. A1 - Toney, Michael F. A1 - Neher, Dieter A1 - Thuc-Quyen Nguyen, T1 - Impact of interfacial molecular orientation on radiative recombination and charge generation efficiency JF - Nature Communications N2 - A long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics-however, the results have important implications on the operation of all optoelectronic devices with donor/ acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting in larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation. Y1 - 2017 U6 - https://doi.org/10.1038/s41467-017-00107-4 SN - 2041-1723 VL - 8 PB - Nature Publ. Group CY - London ER - 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 - Qu, J. Q. A1 - Zhang, J. Y. A1 - Grimsdale, A. C. A1 - Mullen, K. A1 - Jaiser, Frank A1 - Yang, X. H. A1 - Neher, Dieter T1 - Dendronized perylene diimide emitters : Synthesis, luminescence, and electron and energy transfer studies N2 - Aggregation of chromophores in the solid state commonly causes undesirable red shifts in the emission spectra and/or emission quenching. To overcome this problem, we have prepared soluble perylenetetracarboxidiimide dyes in which the chromophores are effectively shielded by polyphenylene dendrimers attached in the bay positions. Models show that attachment of the shielding units in the bay position should provide more efficient shielding than attaching them via the imide moieties. The dendrimers possess excellent film-forming properties due to alkyl substituents on their peripheries. The lack of a red shift in emission upon going from solution to the solid state indicates the dendrons suppress interaction of the emissive cores, leading to pure red-orange emission. Single-layer LEDs produce red-orange emission with relatively low efficiency especially for the higher generation dendrons, which is attributed to poor charge conduction. LEDs using blends of the dendrimers and the undendronized dye as a model compound in PVK have been investigated, and a model to extract relative charge injection rates through the dendritic scaffold from the spectral contributions in the EL spectra is developed Y1 - 2004 SN - 0024-9297 ER - TY - JOUR A1 - Proctor, Christopher M. A1 - Kim, Chunki A1 - Neher, Dieter A1 - Thuc-Quyen Nguyen, T1 - Nongeminate recombination and charge transport limitations in diketopyrrolopyrrole-based solution-processed small molecule solar cells JF - Advanced functional materials N2 - Charge transport and nongeminate recombination are investigated in two solution-processed small molecule bulk heterojunction solar cells consisting of diketopyrrolopyrrole (DPP)-based donor molecules, mono-DPP and bis-DPP, blended with [6,6]-phenyl-C71-butyric acid methyl ester (PCBM). While the bis-DPP system exhibits a high fill factor (62%) the mono-DPP system suffers from pronounced voltage dependent losses, which limit both the fill factor (46%) and short circuit current. A method to determine the average charge carrier density, recombination current, and effective carrier lifetime in operating solar cells as a function of applied bias is demonstrated. These results and light intensity measurements of the current-voltage characteristics indicate that the mono-DPP system is severely limited by nongeminate recombination losses. Further analysis reveals that the most significant factor leading to the difference in fill factor is the comparatively poor hole transport properties in the mono-DPP system (2 x 10(-5) cm(2) V-1 s(-1) versus 34 x 10(-5) cm(2) V-1 s(-1)). These results suggest that future design of donor molecules for organic photovoltaics should aim to increase charge carrier mobility thereby enabling faster sweep out of charge carriers before they are lost to nongeminate recombination. KW - charge transport KW - solar cells KW - photovoltaic devices KW - organic electronics KW - characterization tools Y1 - 2013 U6 - https://doi.org/10.1002/adfm.201202643 SN - 1616-301X SN - 1616-3028 VL - 23 IS - 28 SP - 3584 EP - 3594 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Proctor, Christopher M. A1 - Albrecht, Steve A1 - Kuik, Martijn A1 - Neher, Dieter A1 - Thuc-Quyen Nguyen, T1 - Overcoming geminate recombination and enhancing extraction in solution-processed small molecule solar cells JF - dvanced energy materials Y1 - 2014 U6 - https://doi.org/10.1002/aenm.201400230 SN - 1614-6832 SN - 1614-6840 VL - 4 IS - 10 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Pranav, Manasi A1 - Benduhn, Johannes A1 - Nyman, Mathias A1 - Hosseini, Seyed Mehrdad A1 - Kublitski, Jonas A1 - Shoaee, Safa A1 - Neher, Dieter A1 - Leo, Karl A1 - Spoltore, Donato T1 - Enhanced charge selectivity via anodic-C60 layer reduces nonradiative losses in organic solar cells JF - ACS applied materials & interfaces N2 - Interfacial layers in conjunction with suitable charge-transport layers can significantly improve the performance of optoelectronic devices by facilitating efficient charge carrier injection and extraction. This work uses a neat C-60 interlayer on the anode to experimentally reveal that surface recombination is a significant contributor to nonradiative recombination losses in organic solar cells. These losses are shown to proportionally increase with the extent of contact between donor molecules in the photoactive layer and a molybdenum oxide (MoO3) hole extraction layer, proven by calculating voltage losses in low- and high-donor-content bulk heterojunction device architectures. Using a novel in-device determination of the built-in voltage, the suppression of surface recombination, due to the insertion of a thin anodic-C-60 interlayer on MoO3, is attributed to an enhanced built-in potential. The increased built-in voltage reduces the presence of minority charge carriers at the electrodes-a new perspective on the principle of selective charge extraction layers. The benefit to device efficiency is limited by a critical interlayer thickness, which depends on the donor material in bilayer devices. Given the high popularity of MoO3 as an efficient hole extraction and injection layer and the increasingly popular discussion on interfacial phenomena in organic optoelectronic devices, these findings are relevant to and address different branches of organic electronics, providing insights for future device design. KW - nonradiative losses KW - molybdenum oxide KW - organic solar cells KW - interfacial layers KW - charge selectivity Y1 - 2021 U6 - https://doi.org/10.1021/acsami.1c00049 SN - 1944-8244 SN - 1944-8252 VL - 13 IS - 10 SP - 12603 EP - 12609 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Pralle, Martin U. A1 - Urayama, Kenji A1 - Tew, Gregory N. A1 - Neher, Dieter A1 - Wegner, Gerhard A1 - Stupp, Samuel I. T1 - Piezoelectricity in polar supramolecular materials Y1 - 2000 ER - TY - JOUR A1 - Pradhan, Basudev A1 - Albrecht, Steve A1 - Stiller, Burkhard A1 - Neher, Dieter T1 - Inverted organic solar cells comprising low-temperature-processed ZnO films JF - Applied physics : A, Materials science & processing N2 - Inverted organic solar cells are fabricated using low-temperature-annealed ZnO film as an electron transport layer. Uniform ZnO films were prepared by spin coating a diethylzinc (DEZ) precursor solution in air, followed by annealing at 100 A degrees C. Organic solar cells prepared on these ZnO films with a 1:1 P3HT:PCBM blend as the active layer show a high power conversion efficiency of 4.03 %, which is more than 10 % higher than the PCE of solar cells comprising ZnO prepared via a high-temperature sol-gel route. Y1 - 2014 U6 - https://doi.org/10.1007/s00339-014-8373-8 SN - 0947-8396 SN - 1432-0630 VL - 115 IS - 2 SP - 365 EP - 369 PB - Springer CY - New York ER - TY - JOUR A1 - Poelking, Carl A1 - Benduhn, Johannes A1 - Spoltore, Donato A1 - Schwarze, Martin A1 - Roland, Steffen A1 - Piersimoni, Fortunato A1 - Neher, Dieter A1 - Leo, Karl A1 - Vandewal, Koen A1 - Andrienko, Denis T1 - Open-circuit voltage of organic solar cells BT - interfacial roughness makes the difference JF - Communications physics N2 - Organic photovoltaics (PV) is an energy-harvesting technology that offers many advantages, such as flexibility, low weight and cost, as well as environmentally benign materials and manufacturing techniques. Despite growth of power conversion efficiencies to around 19 % in the last years, organic PVs still lag behind inorganic PV technologies, mainly due to high losses in open-circuit voltage. Understanding and improving open circuit voltage in organic solar cells is challenging, as it is controlled by the properties of a donor-acceptor interface where the optical excitations are separated into charge carriers. Here, we provide an electrostatic model of a rough donor-acceptor interface and test it experimentally on small molecule PV materials systems. The model provides concise relationships between the open-circuit voltage, photovoltaic gap, charge-transfer state energy, and interfacial morphology. In particular, we show that the electrostatic bias generated across the interface reduces the photovoltaic gap. This negative influence on open-circuit voltage can, however, be circumvented by adjusting the morphology of the donor-acceptor interface. Organic solar cells, despite their high power conversion efficiencies, suffer from open circuit voltage losses making them less appealing in terms of applications. Here, the authors, supported with experimental data on small molecule photovoltaic cells, relate open circuit voltage to photovoltaic gap, charge-transfer state energy, and donor-acceptor interfacial morphology. Y1 - 2022 U6 - https://doi.org/10.1038/s42005-022-01084-x SN - 2399-3650 VL - 5 IS - 1 PB - Nature portfolio CY - Berlin ER - TY - JOUR A1 - Pisoni, Stefano A1 - Stolterfoht, Martin A1 - Lockinger, Johannes A1 - Moser, Thierry A1 - Jiang, Yan A1 - Caprioglio, Pietro A1 - Neher, Dieter A1 - Buecheler, Stephan A1 - Tiwari, Ayodhya N. T1 - On the origin of open-circuit voltage losses in flexible n-i-p perovskite solar cells JF - Science and technology of advanced materials : STAM N2 - The possibility to manufacture perovskite solar cells (PSCs) at low temperatures paves the way to flexible and lightweight photovoltaic (PV) devices manufactured via high-throughput roll-to-roll processes. In order to achieve higher power conversion efficiencies, it is necessary to approach the radiative limit via suppression of non-radiative recombination losses. Herein, we performed a systematic voltage loss analysis for a typical low-temperature processed, flexible PSC in n-i-p configuration using vacuum deposited C-60 as electron transport layer (ETL) and two-step hybrid vacuum-solution deposition for CH3NH3PbI3 perovskite absorber. We identified the ETL/absorber interface as a bottleneck in relation to non-radiative recombination losses, the quasi-Fermi level splitting (QFLS) decreases from similar to 1.23 eV for the bare absorber, just similar to 90 meV below the radiative limit, to similar to 1.10 eV when C-60 is used as ETL. To effectively mitigate these voltage losses, we investigated different interfacial modifications via vacuum deposited interlayers (BCP, B4PyMPM, 3TPYMB, and LiF). An improvement in QFLS of similar to 30-40 meV is observed after interlayer deposition and confirmed by comparable improvements in the open-circuit voltage after implementation of these interfacial modifications in flexible PSCs. Further investigations on absorber/hole transport layer (HTL) interface point out the detrimental role of dopants in Spiro-OMeTAD film (widely employed HTL in the community) as recombination centers upon oxidation and light exposure. [GRAPHICS] . KW - Perovskite solar cell KW - flexible KW - interface engineering KW - non-radiative recombination KW - quasi-Fermi level splitting Y1 - 2019 U6 - https://doi.org/10.1080/14686996.2019.1633952 SN - 1468-6996 SN - 1878-5514 VL - 20 SP - 786 EP - 795 PB - Taylor & Francis CY - Abingdon ER - TY - JOUR A1 - Pingel, Patrick A1 - Zen, Achmad A1 - Neher, Dieter A1 - Lieberwirth, Ingo A1 - Wegner, Gerhard A1 - Allard, Sybille A1 - Scherf, Ullrich T1 - Unexpectedly high field-effect mobility of a soluble, low molecular weight oligoquaterthiophene fraction with low polydispersity N2 - Layers made from soluble low molecular weight polythiophene PQT-12 with low polydispersity exhibit a highly ordered structure and charge-carrier mobilities of the order of 10(-3) cm(2)/(V s), which we attribute to its proximity to monodispersity. We propose that polydispersity is a decisive factor with regard to structure formation and transport properties of soluble low molecular weight polythiophenes. Y1 - 2009 UR - http://www.springerlink.com/content/100501 U6 - https://doi.org/10.1007/s00339-008-4994-0 SN - 0947-8396 ER - TY - JOUR A1 - Pingel, Patrick A1 - Arvind, Malavika A1 - Kölln, Lisa A1 - Steyrleuthner, Robert A1 - Kraffert, Felix A1 - Behrends, Jan A1 - Janietz, Silvia A1 - Neher, Dieter T1 - p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane JF - Advanced electronic materials N2 - State-of-the-art p-type doping of organic semiconductors is usually achieved by employing strong -electron acceptors, a prominent example being tetrafluorotetracyanoquinodimethane (F(4)TCNQ). Here, doping of the semiconducting model polymer poly(3-hexylthiophene), P3HT, using the strong Lewis acid tris(pentafluorophenyl)borane (BCF) as a dopant, is investigated by admittance, conductivity, and electron paramagnetic resonance measurements. The electrical characteristics of BCF- and F(4)TCNQ-doped P3HT layers are shown to be very similar in terms of the mobile hole density and the doping efficiency. Roughly 18% of the employed dopants create mobile holes in either F-4 TCNQ- or BCF-doped P3HT, while the majority of doping-induced holes remain strongly Coulomb-bound to the dopant anions. Despite similar hole densities, conductivity and hole mobility are higher in BCF-doped P3HT layers than in F(4)TCNQ-doped samples. This and the good solubility in many organic solvents render BCF very useful for p-type doping of organic semiconductors. KW - charge carrier transport KW - charge transfer KW - conductivity KW - molecular doping KW - organic semiconductors Y1 - 2016 U6 - https://doi.org/10.1002/aelm.201600204 SN - 2199-160X VL - 2 PB - Wiley-Blackwell CY - Hoboken ER -