Publications

2020 – 2024

2015 – 2019

• I. Lange, S. Reiter, M. Pätzel, A. Zykov, A. Nefedov, J. Hildebrandt, S. Hecht, S. Kowarik, C. Wöll, G. Heimel & D. Neher, "Tuning the Work Function of Polar Zinc Oxide Surfaces using Modified Phosphonic Acid Self-Assembled Monolayers", Advanced Functional Materials24, 7014-7024 (2014) DOI • PDF • Supporting Information

  Zinc oxide (ZnO) is regarded as a promising alternative material for transparent conductive electrodes in optoelectronic devices. However, ZnO suffers from poor chemical stability. ZnO also has a moderate work function (WF), which results in substantial charge injection barriers into common (organic) semiconductors that constitute the active layer in a device. Controlling and tuning the ZnO WF is therefore necessary but challenging. Here, a variety of phosphonic acid based self-assembled monolayers (SAMs) deposited on ZnO surfaces are investigated. It is demonstrated that they allow the tuning the WF over a wide range of more than 1.5 eV, thus enabling the use of ZnO as both the hole-injecting and electron-injecting contact. The modified ZnO surfaces are characterized using a number of complementary techniques, demonstrating that the preparation protocol yields dense, well-defined molecular monolayers.

• F. Kraffert, R. Steyrleuthner, S. Albrecht, D. Neher, M.C. Scharber, R. Bittl & J. Behrends, “Charge Separation in PCPDTBT:PCBM Blends from an EPR Perspective”, The Journal of Physical Chemistry C118, 28482–28493 (2014) DOI

  Using time-resolved electron paramagnetic resonance (EPR) spectroscopy in conjunction with optical excitation we study charge separation in conjugated polymers blended with [6,6]-phenyl C61-butyric acid methyl ester (PCBM). A direct comparison between samples comprising poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (C-PCPDTBT) and their analogues containing poly[(4,4′-bis(2-ethylhexyl)dithieno[3,2-b:2′,3′-d]silole)-2,6-diyl-alt-(4,7-bis(2-thienyl)-2,1,3-benzothiadiazole)-5,5′-diyl] (Si-PCPDTBT) reveals a remarkable influence of the bridging atom (carbon vs silicon) in the polymer on the EPR spectra. While the EPR signatures of photogenerated positive polarons in C- and Si-bridged PCPDTBT are virtually identical, significant differences are observed with respect to the spin-relaxation behavior. The spin–lattice relaxation time of positive polarons in C-PCPDTBT at low temperature (T = 80 K) is found to be more than two orders or magnitude longer than in the Si-bridged polymer derivative. This surprisingly slow relaxation can be rationalized by polarons trapped in defect states that seem to be absent (or are present in a substantially smaller concentration) in blends comprising Si-PCPDTBT. Transient EPR signals attributed to charge transfer (CT) states and separated polarons are smaller in the blends with C-PCPDTBT as compared to those with the silicon-bridged polymer. We propose that triplet formation occurs via the CT state, thus diminishing the probability that the CT state forms free charge carriers in blends of C-PCPDTBT with PCBM. This hypothesis is confirmed by direct detection of triplet excitons in C-PCPDTBT:PCBM blends. The shape of the transient EPR spectra reveals that the triplet excitons are, in contrast to those formed in pristine polymer films, not generated by direct intersystem crossing but result from back electron transfer through CT state recombination. The strong triplet signal is not observed in blends containing the Si-bridged polymer, indicating efficient singlet exciton splitting and subsequent charge carrier separation at the Si-PCPDTBT/PCBM interface.

• W. Li, S. Albrecht, L. Yang, S. Roland, J.R. Tumbleston, T. McAfee, L. Yan, M.A. Kelly, H. Ade, D. Neher & W. You, "Mobility-Controlled Performance of Thick Solar Cells Based on Fluorinated Copolymers", Journal of the American Chemical Society136, 15566-15576 (2014) DOI • PDF • Supporting Information • Spotlight

  Developing novel materials and device architectures to further enhance the efficiency of polymer solar cells requires a fundamental understanding of the impact of chemical structures on photovoltaic properties. Given that device characteristics depend on many parameters, deriving structure?property relationships has been very challenging. Here we report that a single parameter, hole mobility, determines the fill factor of several hundred nanometer thick bulk heterojunction photovoltaic devices based on a series of copolymers with varying amount of fluorine substitution. We attribute the steady increase of hole mobility with fluorine content to changes in polymer molecular ordering. Importantly, all other parameters, including the efficiency of free charge generation and the coefficient of nongeminate recombination, are nearly identical. Our work emphasizes the need to achieve high mobility in combination with strongly suppressed charge recombination for the thick devices required by mass production technologies.

• M. Shalom, M. Guttentag, C. Fettkenhauer, S. Inal, D. Neher, A. Llobet & M. Antonietti, "In Situ Formation of Heterojunctions in Modified Graphitic Carbon Nitride: Synthesis and Noble Metal Free Photocatalysis", Chemistry of Materials26, 5812-5818 (2014) DOI

  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.

• J. Xu, T.J.K. Brenner, Z. Chen, D. Neher, M. Antonietti & M. Shalom, "Upconversion-Agent Induced Improvement of g-C3N4 Photocatalyst under Visible Light", ACS Applied Materials & Interfaces6, 16481-16486 (2014) DOI

  Herein, we report the use of upconversion agents to modify graphite carbon nitride (g-C₃N₄) by direct thermal condensation of a mixture of ErCl₃·6H₂O 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.

• D.W. Gehrig, S. Roland, I.A. Howard, V. Kamm, H. Mangold, D. Neher & F. Laquai, “Efficiency-Limiting Processes in Low-Bandgap Polymer:Perylene Diimide Photovoltaic Blends”, The Journal of Physical Chemistry C118, 20077-20085 (2014) DOI

  The charge generation and recombination processes following photoexcitation of a low-bandgap polymer:perylene diimide photovoltaic blend are investigated by transient absorption pump?probe spectroscopy covering a dynamic range from femto- to microseconds to get insight into the efficiency-limiting photophysical processes. The photoinduced electron transfer from the polymer to the perylene acceptor takes up to several tens of picoseconds, and its efficiency is only half of that in a polymer:fullerene blend. This reduces the short-circuit current. Time-delayed collection field experiments reveal that the subsequent charge separation is strongly field-dependent, limiting the fill factor and lowering the short-circuit current in polymer:PDI devices. Upon excitation of the acceptor in the low-bandgap polymer blend, the PDI exciton undergoes charge transfer on a time scale of several tens of picoseconds. However, a significant fraction of the charges generated at the interface are quickly lost because of fast geminate recombination. This reduces the short-circuit current even further, leading to a scenario in which only around 25% of the initial photoexcitations generate free charges that can potentially contribute to the photocurrent. In summary, the key photophysical limitations of perylene diimide as an acceptor in low-bandgap polymer blends appear at the interface between the materials, with the kinetics of both charge generation and separation inhibited as compared to that of fullerenes.

• S. Roland, M. Schubert, B.A. Collins, J. Kurpiers, Z. Chen , A. Facchetti , H. Ade, D. Neher, “Fullerene-Free Polymer Solar Cells with Highly Reduced Bimolecular Recombination and Field-Independent Charge Carrier Generation”, The Journal of Physical Chemistry Letters5, 2815-2822 (2014) DOI

  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.

• S. Schaefer, S. Albrecht, D. Neher, T.F. Schulze, E. Conrad, L. Korte, B. Rech, J. Wördenweber, A. Gordijn, U. Scherf & I. Dumsch, “Electric Field Distribution in Hybrid Solar Cells Comprising an Organic Donor Polymer and Amorphous Silicon”, Organic Photonics and Photovoltaics2, 12-20 (2014) DOI • PDF

  We present a study on the performance and analysis of hybrid solar cells comprising a planar heterojunction between between a conjugated donor polymer, P3HT or PCPDTBT, and hydrogenated amorphous silicon (a-Si:H). A comparison of the modeled absorption spectra of the layer stack with the measured external quantum efficiency is used to investigate the contribution of the inorganic and organic material to the photocurrent generation in the device. Although both materials contribute to the photocurrent, the devices exhibit poor quantum efficiencies and low short circuit currents. Bandstructure simulations of the hybrid layer structure reveal that an unfavorable electric field distribution within the planar multilayer structure limits the performance. Using electroabsorption measurements we can show that the electric field is extremelyweak in the amorphous silicon but strong in the organic material. The situation changes drasticallywhen the conjugated polymer is p-doped. Doping not only increases the conductivity of the organic material, but also restores the electric field in the amorphous silicon layer. Optimized hybrid solar cells comprising thin doped P3HT layers exhibit energy conversion efficiencies (ECE) up to 2.8%.

• R. Di Pietro, D. Venkateshvaran, A. Klug, E.J.W. List-Kratochvil, A. Facchetti, H. Sirringhaus, D. Neher, “Simultaneous extraction of charge density dependent mobility and variable contact resistance from thin film transistors”, Applied Physics Letters104, 193501 (2014) DOI • PDF

  A model for the extraction of the charge density dependent mobility and variable contact resistance in thin film transistors is proposed by performing a full derivation of the current-voltage characteristics both in the linear and saturation regime of operation. The calculated values are validated against the ones obtained from direct experimental methods. This approach allows unambiguous determination of gate voltage dependent contact and channel resistance from the analysis of a single device. It solves the inconsistencies in the commonly accepted mobility extraction methods and provides additional possibilities for the analysis of the injection and transport processes in semiconducting materials.

• M. Schubert, B.A. Collins, H. Mangold, I.A. Howard, W. Schindler, K. Vandewal, S. Roland, J. Behrends, F. Kraffert, R. Steyrleuthner, Z. Chen, K. Fostiropoulos, R. Bittl, A. Salleo, A. Facchetti, F. Laquai, H.W. Ade, D. Neher, “Correlated Donor/Acceptor Crystal Orientation Controls Photocurrent Generation in All-Polymer Solar Cells”, Advanced Functional Materials24, 4068-4081 (2014) DOI

  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, efficient 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.

• S. Albrecht, B. Grootoonk, S. Neubert, S. Roland, J. Wördenweber, M. Meier, R. Schlatmann, A. Gordijn, D. Neher, “Efficient hybrid inorganic/organic tandem solar cells with tailored recombination contacts”, Solar Energy Materials and Solar Cells127, 157-162 (2014) DOI

  In this work, the authors present a 7.5% efficient hybrid tandem solar cell with the bottom cell made of amorphous silicon and a Si-PCPDTBT:PC₇₀BM bulk heterojunction top cell. Loss-free recombination contacts were realized by combing Al-doped ZnO with either the conducting polymer composite PEDOT:PSS or with a bilayer of ultrathin Al and MoO₃. Optimization of these contacts results in tandem cells with high fill factors of 70% and an open circuit voltage close to the sum of those of the sub-cells. This is the best efficiency reported for this type of hybrid tandem cell so far. Optical and electrical device modeling suggests that the efficiency can be increased to ~12% on combining a donor polymer with suitable absorption onset with PCBM. We also describe proof-of-principle studies employing light trapping in hybrid tandem solar cells, suggesting that this device architecture has the potential to achieve efficiencies well above 12%.

• B. Pradhan, S. Albrecht, B. Stiller & D. Neher, “Inverted organic solar cells comprising low-temperature-processed ZnO films”, Applied Physics A115, 365-369 (2014) DOI

  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°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.

• J. Kniepert, I. Lange, N.J. van der Kaap, L.A.J. Koster, D. Neher, “A conclusive view on charge generation, recombination and extraction in as-prepared and annealed P3HT:PCBM blends: A combined experimental-simulation work”, Advanced Energy Materials4, 1301401 (2014) DOI

  Time-delayed collection field (TDCF) and bias-amplified charge extraction (BACE) are applied to as-prepared and annealed poly(3-hexylthiophene):[6,6]-phenyl C₇₁ butyric acid methyl ester (P3HT:PCBM) blends coated from chloroform. Despite large differences in fill factor, short-circuit current, and power conversion efficiency, both blends exhibit a negligible dependence of photogeneration on the electric field and strictly bimolecular recombination (BMR) with a weak dependence of the BMR coefficient on charge density. Drift-diffusion simulations are performed using the measured coefficients and mobilities, taking into account bimolecular recombination and the possible effects of surface recombination. The excellent agreement between the simulation and the experimental data for an intensity range covering two orders of magnitude indicates that a field-independent generation rate and a density-independent recombination coefficient describe the current–voltage characteristics of the annealed P3HT:PCBM devices, while the performance of the as-prepared blend is shown to be limited by space charge effects due to a low hole mobility. Finally, even though the bimolecular recombination coefficient is small, surface recombination is found to be a negligible loss mechanism in these solar cells.

• S. Albrecht, K. Vandewal, J.R. Tumbleston, F.S.U. Fischer, J.D. Douglas, J.M.J. Fréchet, S. Ludwigs, H. Ade, A. Salleo, D. Neher, “On the Efficiency of Charge Transfer State Splitting in Polymer:Fullerene Solar Cells”, Advanced Materials26, 2533-2539 (2014) DOI • Inside Back Cover

  The field dependence and yield of free charge carrier generation in polymer:fullerene blends with varying energetic offsets is not affected when the excitation energy is varied from above band-gap to direct CT state excitation. Instead, the ability of the CT state to split is dictated by the energetic offset between the relaxed CT state and the charge separated (CS) state.

• M. Shalom, S. Inal, D. Neher, M. Antonietti, “SiO₂/carbon nitride composite materials: The role of surfaces for enhanced photocatalysis”, Catalysis Today225, 185-190 (2014) DOI

  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.

• K. Tremel, F.S.U. Fischer, N. Kayunkid, R. Di Pietro, R. Tkachov, A. Kiriy, D. Neher, S. Ludwigs, M. Brinkmann, “Charge Transport Anisotropy in Highly Oriented Thin Films of the Acceptor Polymer P(NDI2OD-T2)”, Advanced Energy Materials4, 1301659 (2014) DOI

  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 cm²/Vs are observed parallel to the polymer chain, which is up to 10 times higher than those perpendicular to the polymer chain.

• C.M. Proctor, S. Albrecht, M. Kuik, D. Neher, T.-Q. Nguyen, “Overcoming Geminate Recombination and Enhancing Extraction in Solution-Processed Small Molecule Solar Cells”, Advanced Energy Materials4, 1400230 (2014) DOI

  The effects of processing conditions on charge transport and voltage dependent recombination losses in one of the most efficient solution-processed small molecule solar cell systems reported to date are studied. With careful control of the blend film morphology, geminate recombination (GR) can be completely overcome while reducing bimolecular recombination (BMR) to allow for efficient generation and collection of photogenerated charge carriers. These results highlight that a field-dependent generation mechanism is not necessarily an inherent molecular property.

• S. Albrecht, J.R. Tumbleston, S. Janietz, I. Dumsch, S. Allard, U. Scherf, H. Ade, D. Neher, “Quantifying Charge Extraction in Organic Solar Cells: The Case of Fluorinated PCPDTBT”, The Journal of Physical Chemistry Letters5, 1131-1138 (2014) DOI

  We introduce a new and simple method to quantify the effective extraction mobility in organic solar cells at low electric fields and charge carrier densities comparable to operation conditions under one sun illumination. By comparing steady-state carrier densities at constant illumination intensity and under open-circuit conditions, the gradient of the quasi-Fermi potential driving the current is estimated as a function of external bias and charge density. These properties are then related to the respective steady-state current to determine the effective extraction mobility. The new technique is applied to different derivatives of the well-known low-band-gap polymer PCPDTBT blended with PC70BM. We show that the slower average extraction due to lower mobility accounts for the moderate fill factor when solar cells are fabricated with mono- or difluorinated PCPDTBT. This lower extraction competes with improved generation and reduced nongeminate recombination, rendering the monofluorinated derivative the most efficient donor polymer.

• A. Foertig, J. Kniepert, M. Gluecker, T. Brenner, V. Dyakonov, D. Neher, C. Deibel, “Nongeminate and Geminate Recombination in PTB7:PCBM Solar Cells”, Advanced Functional Materials24, 1306-1311 (2014) DOI

  A combination of transient photovoltage (TPV), voltage dependent charge extraction (CE), and time delayed collection field (TDCF) measurements is applied to poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl] [3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]thiophenediyl]] (PTB7):[6,6]-phenyl-C71-butyric acid (PC₇₁BM) bulk heterojunction solar cells to analyze the limitations of photovoltaic performance. Devices are processed from pure chlorobenzene (CB) solution and a subset is optimized with 1,8-diiodooctane (DIO) as co-solvent. The dramatic changes in device performance are discussed with respect to the dominating loss processes. While in the devices processed from CB solution severe geminate and nongeminate recombination is observed, the use of DIO facilitates efficient polaron pair dissociation and minimizes geminate recombination. Thus, from the determined charge carrier decay rate under open circuit conditions and the voltage dependent charge carrier densities n(V), the nongeminate loss current J_loss of the samples with DIO alone enables the reconstruction of the current/voltage (j/V) characteristics across the whole operational voltage range. Geminate and nongeminate losses are considered to describe the j/V response of cells prepared without additive, but lead to a clearly overestimated device performance. The deviation between measured and reconstructed j/V characteristics is attributed to trapped charges in isolated domains of pure fullerene phases.

• R. Steyrleuthner, R. Di Pietro, B.A. Collins, F. Polzer, S. Himmelberger, M. Schubert, Z. Chen, S. Zhang, A. Salleo, H. Ade, A. Facchetti, D. Neher, “The Role of Regioregularity, Crystallinity, and Chain Orientation on Electron Transport in a High-Mobility n-Type Copolymer”, Journal of the American Chemical Society136, 4245-4256 (2014) DOI

  We investigated the correlation between the polymer backbone structural regularity and the charge transport properties of poly{[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} [P(NDI2OD-T2)], a widely studied semiconducting polymer exhibiting high electron mobility and an unconventional micromorphology. To understand the influence of the chemical structure and crystal packing of conventional regioregular P(NDI2OD-T2) [RR-P(NDI2OD-T2)] on the charge transport, the corresponding regioirregular polymer RI-P(NDI2OD-T2) was synthesized. By combining optical, X-ray, and transmission electron microscopy data, we quantitatively characterized the aggregation, crystallization, and backbone orientation of all of the polymer films, which were then correlated to the electron mobilities in electron-only diodes. By carefully selecting the preparation conditions, we were able to obtain RR-P(NDI2OD-T2) films with similar crystalline structure along the three crystallographic axes but with different orientations of the polymer chains with respect to the substrate surface. RI-P(NDI2OD-T2), though exhibiting a rather similar LUMO structure and energy compared with the regioregular counterpart, displayed a very different packing structure characterized by the formation of ordered stacks along the lamellar direction without detectible π-stacking. Vertical electron mobilities were extracted from the space-charge-limited currents in unipolar devices. We demonstrate the anisotropy of the charge transport along the different crystallographic directions and how the mobility depends on π-stacking but is insensitive to the degree or coherence of lamellar stacking. The comparison between the regioregular and regioirregular polymers also shows how the use of large planar functional groups leads to improved charge transport, with mobilities that are less affected by chemical and structural disorder with respect to classic semicrystalline polymers such as poly(3-hexylthiophene).

• W. Liu, R. Tkachov, H. Komber, V. Senkovskyy, M. Schubert, Z. Wei, A. Facchetti, D. Neher, A. Kiriy, “Chain-growth polycondensation of perylene diimide-based copolymers: a new route to regio-regular perylene diimide-based acceptors for all-polymer solar cells and n-type transistors”, Polymer Chemistry5, 3404-3411 (2014) DOI

  Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to Mw≈50 kg/mol and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32-45%) in all-polymer solar cells compared to NDI-based materials (15-30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells.

• K. Vandewal, S. Albrecht, E.T. Hoke, K.R. Graham, J. Widmer, J.D. Douglas, M. Schubert, W.R. Mateker, J.T. Bloking, G.F. Burkhard, A. Sellinger, J.M.J. Fréchet, A. Amassian, M.K. Riede, M.D. McGehee, D. Neher, A. Salleo, “Efficient charge generation by relaxed charge-transfer states at organic interfaces”, Nature Materials13, 63-68 (2014) DOI

  Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge 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 via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C₆₀ 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.

• I. Lange, J. Kniepert, P. Pingel, I. Dumsch, S. Allard, S. Janietz, U. Scherf & D. Neher, “Correlation between the Open Circuit Voltage and the Energetics of Organic Bulk Heterojunction Solar Cells”, The Journal of Physical Chemistry Letters4, 3865 (2013) DOI

  A detailed investigation of the open circuit voltage (V_OC) of organic bulk heterojunction solar cells comprising three different donor polymers and two different fullerene-based acceptors is presented. Bias amplified charge extraction (BACE) is combined with Kelvin Probe measurements to derive information on the relevant energetics in the blend. On the example of P3HT:PC₇₀BM the influence of composition and preparation conditions on the relevant transport levels will be shown. Moderate upward shifts of the P3HT HOMO depending on crystallinity are observed, but contrarily to common believe, the dependence of V_OC on blend composition and thermal history is found to be largely determined by the change in the PCBM LUMO energy. Following this approach, we quantified the energetic contribution to the V_OC in blends with fluorinated polymers or higher adduct fullerenes.

• S. Inal, L. Chiappisi, J.D. Kölsch, M. Kraft, M.-S. Appavou, U. Scherf, M. Wagner, M.R. Hansen, M. Gradzielski, A. Laschewsky & D. Neher, “Temperature-Regulated Fluorescence and Association of an Oligo(ethyleneglycol)methacrylate-Based Copolymer with a Conjugated Polyelectrolyte – The Effect of Solution Ionic Strength”, The Journal of Physical Chemistry B117, 14576 (2013) DOI

  Aqueous mixtures of a dye-labeled non-ionic thermoresponsive copolymer and a conjugated cationic polyelectrolyte are shown to exhibit characteristic changes in fluorescence properties in response to temperature and to the presence of salts, enabling a double-stimuli responsiveness. In such mixtures at room temperature, i.e., well below the lower critical solution temperature (LCST), the emission of the dye is strongly quenched due to energy transfer to the polycation, pointing to supramolecular interactions between the two macromolecules. Increasing the concentration of salts weakens the interpolymer interactions, the extent of which is simultaneously monitored from the change in the relative emission intensity of the components. When the mixture is heated above its LCST, the transfer efficiency is significantly reduced, signaling a structural reorganization process, however, surprisingly only if the mixture contains salt ions. To elucidate the reasons behind such thermo- and ion-sensitive fluorescence characteristics, we investigate the effect of salts of alkali chlorides, in particular of NaCl, on the association behavior of these macromolecules before and after the polymer phase transition by a combination of UV-vis, fluorescence, and ¹H NMR spectroscopy with light scattering and small-angle neutron scattering measurements.

• S. Inal, J.D. Kölsch, F. Sellrie, J.A. Schenk, E. Wischerhoff, A. Laschewsky & D. Neher, “A water soluble fluorescent polymer as a dual colour sensor for temperature and a specific protein”, Journal of Materials Chemistry B1, 6373 (2013) DOI

  We present two thermoresponsive water soluble copolymers prepared via free radical statistical copolymerization of N-isopropylacrylamide (NIPAm) and of oligo(ethylene glycol) methacrylates (OEGMAs), respectively, with a solvatochromic 7-(diethylamino)-3-carboxy-coumarin (DEAC)-functionalized monomer. In aqueous solutions, the NIPAm-based copolymer exhibits characteristic changes in its fluorescence profile in response to a change in solution temperature as well as to the presence of a specific protein, namely an anti-DEAC antibody. This polymer emits only weakly at low temperatures, but exhibits a marked fluorescence enhancement accompanied by a change in its emission colour when heated above its cloud point. Such drastic changes in the fluorescence and absorbance spectra are observed also upon injection of the anti-DEAC antibody, attributed to the specific binding of the antibody to DEAC moieties. Importantly, protein binding occurs exclusively when the polymer is in the well hydrated state below the cloud point, enabling a temperature control on the molecular recognition event. On the other hand, heating of the polymer-antibody complexes releases a fraction of the bound antibody. In the presence of the DEAC-functionalized monomer in this mixture, the released antibody competitively binds to the monomer and the antibody-free chains of the polymer undergo a more effective collapse and inter-aggregation. In contrast, the emission properties of the OEGMA-based analogous copolymer are rather insensitive to the thermally induced phase transition or to antibody binding. These opposite behaviours underline the need for a carefully tailored molecular design of responsive polymers aimed at specific applications, such as biosensing.

• S. Inal, J.D. Kölsch, L. Chiappisi, D. Janietz, M. Gradzielski, A. Laschewsky, D. Neher, “Structure-related differences in the temperature-regulated fluorescence response of LCST type polymers”, Journal of Materials Chemistry C1, 6603 (2013) DOI

  We demonstrate new fluorophore-labelled materials based on acrylamide and on oligo(ethylene glycol) (OEG) bearing thermoresponsive polymers for sensing purposes and investigate their thermally induced solubility transitions. It is found that the emission properties of the polarity-sensitive (solvatochromic) naphthalimide derivative attached to three different thermoresponsive polymers are highly specific to the exact chemical structure of the macromolecule. While the dye emits very weakly below the LCST when incorporated into poly(N-isopropylacrylamide) (pNIPAm) or into a polyacrylate backbone bearing only short OEG side chains, it is strongly emissive in polymethacrylates with longer OEG side chains. Heating of the aqueous solutions above their cloud point provokes an abrupt increase of the fluorescence intensity of the labelled pNIPAm, whereas the emission properties of the dye are rather unaffected as OEG-based polyacrylates and methacrylates undergo phase transition. Correlated with laser light scattering studies, these findings are ascribed to the different degrees of pre-aggregation of the chains at low temperatures and to the extent of dehydration that the phase transition evokes. It is concluded that although the temperature-triggered changes in the macroscopic absorption characteristics, related to large-scale alterations of the polymer chain conformation and aggregation, are well detectable and similar for these LCST-type polymers, the micro-environment provided to the dye within each polymer network differs substantially. Considering sensing applications, this finding is of great importance since the temperature-regulated fluorescence response of the polymer depends more on the macromolecular architecture than the type of reporter fluorophore.

• M. Shalom, S. Inal, C. Fettkenhauer, D. Neher, M. Antonietti, "Improving Carbon Nitride Photocatalysis by Supramolecular Preorganization of Monomers", Journal of the American Chemical Society135, 7118 (2013) DOI

  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.

• P. Pingel, D. Neher, “Comprehensive picture of p-type doping of P3HT with the molecular acceptor F₄TCNQ”, Physical Review B87, 115209 (2013) DOI • PDF • Supporting Information

  By means of optical spectroscopy, Kelvin probe, and conductivity measurements, we study the p-type doping of the donor polymer poly(3-hexylthiophene), P3HT, with the molecular acceptor tetrafluorotetracyanoquinodimethane, F₄TCNQ, covering a broad range of molar doping ratios from the ppm to the percent regime. Thorough quantitative analysis of the specific near-infrared absorption bands of ionized F₄TCNQ reveals that almost every F₄TCNQ dopant undergoes integer charge transfer with a P3HT site. However, only about 5% of these charge carrier pairs are found to dissociate and contribute a free hole for electrical conduction. The nonlinear behavior of the conductivity on doping ratio is rationalized by a numerical mobility model that accounts for the broadening of the energetic distribution of transport sites by the Coulomb potentials of ionized F₄TCNQ dopants.

• G. Lu, J. Blakesley, S. Himmelberger, P. Pingel, J. Frisch, I. Lieberwirth, I. Salzmann, M. Oehzelt, R. Di Pietro, A. Salleo, N. Koch, D. Neher, “Moderate doping leads to high performance of semiconductor/insulator polymer blend transistors”, Nature Communications4, 1588 (2013) DOI • PDF • Supporting Information

  Polymer transistors are being intensively developed for next-generation flexible electronics. Blends comprising a small amount of semiconducting polymer mixed into an insulating polymer matrix have simultaneously shown superior performance and environmental stability in organic field-effect transistors compared with the neat semiconductor. Here we show that such blends actually perform very poorly in the undoped state, and that mobility and on/off ratio are improved dramatically upon moderate doping. Structural investigations show that these blend layers feature nanometre-scale semiconductor domains and a vertical composition gradient. This particular morphology enables a quasi three-dimensional spatial distribution of semiconductor pathways within the insulating matrix, in which charge accumulation and depletion via a gate bias is substantially different from neat semiconductor, and where high on-current and low off-current are simultaneously realized in the stable doped state. Adding only 5 wt% of a semiconducting polymer to a polystyrene matrix, we realized an environmentally stable inverter with gain up to 60.

• S. Inal, J.D. Kölsch, L. Chiappisi, M. Kraft, A. Gutacker, D. Janietz, U. Scherf, M. Gradzielski, A. Laschewsky & D. Neher, “Temperature-Regulated Fluorescence Characteristics of Supramolecular Assemblies Formed By a Smart Polymer and a Conjugated Polyelectrolyte”, Macromolecular Chemistry and Physics214, 435 (2013) DOI

  Aqueous mixtures of a coumarin-labeled non-ionic thermoresponsive copolymer and a cationic polythiophene exhibit marked changes in their fluorescence properties upon heating. At room temperature, emission from the label is significantly quenched due to energy transfer to the conjugated polyelectrolyte. Heating the mixture reduces the energy-transfer efficiency markedly, resulting in a clearly visible change of the emission color. Although the two macromolecules associate strongly at room temperature, the number of interacting sites is largely reduced upon the phase transition. Crucially, the intermolecular association does not suppress the responsiveness of the smart polymer, meaning that this concept should be applicable to chemo- or bioresponsive polymers with optical read-out, for example, as a sensor device.

• C.M. Proctor, C. Kim, D. Neher & T.-Q. Nguyen, “Nongeminate Recombination and Charge Transport Limitations in Diketopyrrolopyrrole-Based Solution-Processed Small Molecule Solar Cells”, Advanced Functional Materials23, 3584 (2013) DOI

  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 (2×10⁻⁵ cm²/Vs versus 34×10⁻⁵ cm²/Vs). 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.

• H. Li, S.S. Babu, S.T. Turner, D. Neher, M.J. Hollamby, T. Seki, S. Yagai, Y. Deguchi, H. Möhwald & T. Nakanishi, “Alkylated-C₆₀ based soft materials: regulation of self-assembly and optoelectronic properties by chain branching”, Journal of Materials Chemistry C1, 1943 (2013) DOI

  Derivatization of fullerene (C₆₀) with branched aliphatic chains softens C₆₀-based materials and enables the formation of thermotropic liquid crystals and room temperature nonvolatile liquids. This work demonstrates that by carefully tuning parameters such as type, number and substituent position of the branched chains, liquid crystalline C₆₀ materials with mesophase temperatures suited for photovoltaic cell fabrication and room temperature nonvolatile liquid fullerenes with tunable viscosity can be obtained. In particular, compound 1, with branched chains, exhibits a smectic liquid crystalline phase extending from 84°C to room temperature. Analysis of bulk heterojunction (BHJ) organic solar cells with a ca. 100 nm active layer of compound 1 and poly(3-hexylthiophene) (P3HT) as an electron acceptor and an electron donor, respectively, reveals an improved performance (power conversion efficiency, PCE: 1.6±0.1%) in comparison with another compound, 10 (PCE: 0.5±0.1%). The latter, in contrast to 1, carries linear aliphatic chains and thus forms a highly ordered solid lamellar phase at room temperature. The solar cell performance of 1 blended with P3HT approaches that of PCBM/P3HT for the same active layer thickness. This indicates that C₆₀ derivatives bearing branched tails are a promising class of electron acceptors in soft (flexible) photovoltaic devices.

• S.T. Hoffmann, F. Jaiser, A. Hayer, H. Bässler, T. Unger, S. Athanasopoulos, D. Neher & A. Köhler, “How Do Disorder, Reorganization, and Localization Influence the Hole Mobility in Conjugated Copolymers?”, Journal of the American Chemical Society135, 1772 (2013) DOI

  In order to unravel the intricate interplay between disorder effects, molecular reorganization, and charge carrier localization, a comprehensive study was conducted on hole transport in a series of conjugated alternating phenanthrene indenofluorene copolymers. Each polymer in the series contained one further comonomer comprising monoamines, diamines, or amine-free structures, whose influence on the electronic, optical, and charge transport properties was studied. The series covered a wide range of highest occupied molecular orbital (HOMO) energies as determined by cyclovoltammetry. The mobility, inferred from time-of-flight (ToF) experiments as a function of temperature and electric field, was found to depend exponentially on the HOMO energy. Since possible origins for this effect include energetic disorder, polaronic effects, and wave function localization, the relevant parameters were determined using a range of methods. Disorder and molecular reorganization were established first by an analysis of absorption and emission measurements and second by an analysis of the ToF measurements. In addition, density functional theory calculations were carried out to determine how localized or delocalized holes on a polymer chain are and to compare calculated reorganization energies with those that have been inferred from optical spectra. In summary, we conclude that molecular reorganization has little effect on the hole mobility in this system while both disorder effects and hole localization in systems with low-lying HOMOs are predominant. In particular, as the energetic disorder is comparable for the copolymers, the absolute value of the hole mobility at room temperature is determined by the hole localization associated with the triarylamine moieties.

• M. Schubert, E. Preis, J.C. Blakesley, P. Pingel, U. Scherf & D. Neher, "Mobility relaxation and electron trapping in a donor/acceptor copolymer", Physical Review B87, 024203 (2013) DOI • PDF • Supporting Information

  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.

• B.C.D. Salert, H. Krueger, S.A. Bagnich, T. Unger, F. Jaiser, M. Al-Sa'di, D. Neher, A. Hayer & T. Eberle, "New polymer matrix system for phosphorescent organic light-emitting diodes and the role of the small molecular co-host", Journal of Polymer Science Part A: Polymer Chemistry51, 601 (2013) DOI

  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/m². 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°C. We also show that the long-time degradation must be related to a change of the optical and electrical bulk properties.

• S. Schattauer, B. Reinhold, S. Albrecht, C. Fahrenson, M. Schubert, S. Janietz & D. Neher, "Influence of sintering on the structural and electronic properties of TiO2 nanoporous layers prepared via a non-sol–gel approach", Colloid and Polymer Science290, 1843 (2012) DOI

  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°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 2×10⁻⁶ to 3×10⁻⁵ cm²/Vs when the sinter temperature is increased from 400 to 600°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°C, while the polymer penetrated deeply into titania layers that were sintered at 600°C. Best photovoltaic performance was reached with a nanoporous TiO₂ film sintered at 550°C, which yielded a power conversion efficiency of 0.5 %. Noticeably, samples with the TiO₂ layer dried at 120°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.

• R. Steyrleuthner, M. Schubert, I.A. Howard, B. Klaumünzer, K. Schilling, Z. Chen, P. Saalfrank, F. Laquai, A. Facchetti & D. Neher, "Aggregation in a High Mobility n-type Low Bandgap Copolymer with Implications on Semicrystalline Morphology", Journal of the American Chemical Society134, 18303 (2012) DOI

  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 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 suggests that aggregation is a two-step process with different types of aggregates which we confirm by time-dependent photoluminescence measurements. Analytical ultracentrifugation measurements demonstrate 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 ~45%. This process also inhibits the formation of amorphous and disordered P(NDI2OD-T2) films.

• M. Al-Sa'di, F. Jaiser, S. Bagnich, T. Unger, J. Blakesley, A. Wilke & D. Neher, "Electrical and optical simulations of a polymer-based phosphorescent organic light-emitting diode with high efficiency", Journal of Polymer Science Part B: Polymer Physics50, 1567 (2012) DOI

  A comprehensive numerical device simulation of the electrical and optical characteristics accompanied with experimental measurements of a new highly efficient system for polymer-based light-emitting diodes doped with phosphorescent dyes is presented. The system under investigation comprises an electron transporter attached to a polymer backbone blended with an electronically inert small molecule and an iridium-based green phosphorescent dye which serves as both emitter and hole transporter. The device simulation combines an electrical and an optical model. Based on the known highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels of all components as well as the measured electrical and optical characteristics of the devices, we model the emissive layer as an effective medium using the dye's HOMO as hole transport level and the polymer LUMO as electron transport level. By fine-tuning the injection barriers at the electron and hole-injecting contact, respectively, in simulated devices, unipolar device characteristics were fitted to the experimental data. Simulations using the so-obtained set of parameters yielded very good agreement to the measured current–voltage, luminance–voltage characteristics, and the emission profile of entire bipolar light-emitting diodes, without additional fitting parameters. The simulation was used to gain insight into the physical processes and the mechanisms governing the efficiency of the organic light-emitting diode, including the position and extent of the recombination zone, carrier concentration profiles, and field distribution inside the device. The simulations show that the device is severely limited by hole injection, and that a reduction of the hole-injection barrier would improve the device efficiency by almost 50%.

• S. Albrecht, S. Janietz, W. Schindler, J. Frisch, J. Kurpiers, J. Kniepert, S. Inal, P. Pingel, K. Fostiropoulos, N. Koch & D. Neher, “Fluorinated Copolymer PCPDTBT with Enhanced Open-Circuit Voltage and Reduced Recombination for Highly Efficient Polymer Solar Cells”, Journal of the American Chemical Society134, 14932 (2012) DOI

  A novel fluorinated copolymer (F-PCPDTBT) is introduced and shown to exhibit significantly higher power conversion efficiency in bulk heterojunction solar cells with PC70BM compared to the well-known low-band-gap polymer PCPDTBT. Fluorination lowers the polymer HOMO level, resulting in high open-circuit voltages well exceeding 0.7 V. Optical spectroscopy and morphological studies with energy-resolved transmission electron microscopy reveal that the fluorinated polymer aggregates more strongly in pristine and blended layers, with a smaller amount of additives needed to achieve optimum device performance. Time-delayed collection field and charge extraction by linearly increasing voltage are used to gain insight into the effect of fluorination on the field dependence of free charge-carrier generation and recombination. F-PCPDTBT is shown to exhibit a significantly weaker field dependence of free charge-carrier generation combined with an overall larger amount of free charges, meaning that geminate recombination is greatly reduced. Additionally, a 3-fold reduction in non-geminate recombination is measured compared to optimized PCPDTBT blends. As a consequence of reduced non-geminate recombination, the performance of optimized blends of fluorinated PCPDTBT with PC₇₀BM is largely determined by the field dependence of free-carrier generation, and this field dependence is considerably weaker compared to that of blends comprising the non-fluorinated polymer. For these optimized blends, a short-circuit current of 14 mA/cm², an open-circuit voltage of 0.74 V, and a fill factor of 58% are achieved, giving a highest energy conversion efficiency of 6.16%. The superior device performance and the low band-gap render this new polymer highly promising for the construction of efficient polymer-based tandem solar cells.

• P. Pingel, R. Schwarzl & D. Neher, “Effect of molecular p-doping on hole density and mobility in poly(3-hexylthiophene)”, Applied Physics Letters100, 143303 (2012) DOI • PDF • Supporting Information

  Employing impedance spectroscopy, we have studied the hole density, conductivity, and mobility of poly(3-hexylthiophene), P3HT, doped with the strong molecular acceptor tetrafluorotetracyanoquinodimethane, F₄TCNQ. We find that the hole density increases linearly with the F₄TCNQ concentration. Furthermore, the hole mobility is decreased upon doping at low-to-medium doping level, which is rationalized by an analytic model of carrier mobility in doped organic semiconductors [V. I. Arkhipov, E. V. Emelianova, P. Heremans, and H. Bässler, Phys. Rev. B 72, 235202 (2005)]. We infer that the presence of ionized F₄TCNQ molecules in the P3HT layer increases energetic disorder, which diminishes the carrier mobility.

• S. Albrecht, W. Schindler, J. Kurpiers, J. Kniepert, J.C. Blakesley, I. Dumsch, S. Allard, K. Fostiropoulos, U. Scherf & D. Neher, “On the Field Dependence of Free Charge Carrier Generation and Recombination in Blends of PCPDTBT/PC₇₀BM: Influence of Solvent Additives”, The Journal of Physical Chemistry Letters 3, 640 (2012) DOI

  We have applied time-delayed collection field (TDCF) and charge extraction by linearly increasing voltage (CELIV) to investigate the photogeneration, transport, and recombination of charge carriers in blends composed of PCPDTBT/PC₇₀BM processed with and without the solvent additive diiodooctane. The results suggest that the solvent additive has severe impacts on the elementary processes involved in the photon to collected electron conversion in these blends. First, a pronounced field dependence of the free carrier generation is found for both blends, where the field dependence is stronger without the additive. Second, the fate of charge carriers in both blends can be described with a rather high bimolecular recombination coefficients, which increase with decreasing internal field. Third, the mobility is three to four times higher with the additive. Both blends show a negative field dependence of mobility, which we suggest to cause bias-dependent recombination coefficients.

• M. Schubert, D. Dolfen, J. Frisch, S. Roland, R. Steyrleuthner, B. Stiller, Z. Chen, U. Scherf, N. Koch, A. Facchetti & D. Neher, “Influence of Aggregation on the Performance of All-Polymer Solar Cells Containing Low-Bandgap Naphthalenediimide Copolymers”, Advanced Energy Materials2, 369 (2012) DOI

  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 donor–acceptor heterojunction.

• S. Albrecht, S. Schäfer, I. Lange, S. Yilmaz, I. Dumsch, S. Allard, U. Scherf, A. Hertwig & D. Neher, “Light management in PCPDTBT:PC70BM solar cells: A comparison of standard and inverted device structures”, Organic Electronics13, 615 (2012) DOI

  We compare standard and inverted bulk heterojunction solar cells composed of PCPDTBT:PC₇₀BM blends. Inverted devices comprising 100 nm thick active layers exhibited short circuit currents of 15 mA/cm², 10% larger than in corresponding standard devices. Modeling of the optical field distribution in the different device stacks proved that this enhancement originates from an increased absorption of incident light in the active layer. Internal quantum efficiencies (IQEs) were obtained from the direct comparison of experimentally derived and modeled currents for different layer thicknesses, yielding IQEs of about 70% for a layer thickness of 100 nm. Simulations predict a significant increase of the light harvesting efficiency upon increasing the layer thickness to 270 nm. However, a continuous deterioration of the photovoltaic properties with layer thickness was measured for both device architectures, attributed to incomplete charge extraction. On the other hand, our optical modeling suggests that inverted devices based on PCPDTBT should be able to deliver high power conversion efficiencies (PCEs) of more than 7% provided that recombination losses can be reduced.

• C. Scharsich, R.H. Lohwasser, M. Sommer, U. Asawapirom, U. Scherf, M. Thelakkat, D. Neher & A. Köhler, “Control of aggregate formation in poly(3-hexylthiophene) by solvent, molecular weight, and synthetic method”, Journal of Polymer Science Part B: Polymer Physics50, 442 (2012) DOI

  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.

• J. Frisch, M. Schubert, E. Preis, J.P. Rabe, D. Neher, U. Scherf & N. Koch, "Full electronic structure across a polymer heterojunction solar cell", Journal of Materials Chemistry22, 4418 (2012) DOI

  We correlate the morphology and energy level alignment of bilayer structures comprising the donor poly(3-hexylthiophene) (P3HT) and the acceptor polyfluorene copolymer poly(9,9'dialklylfluorene-alt-4,7-bis(2,5-thiendiyl)-2,1,3-benzothiadiazole) (PFTBTT) with the performance of these bilayers in organic photovoltaic cells (OPVCs). The conducting polymer poly(ethylenedioxythiophene):poly(styrenesulfonate) (PEDT:PSS) was used as the bottom electrode and Ca as the top electrode. Ultraviolet photoelectron spectroscopy (UPS) revealed that notable interface dipoles occur at all interfaces across the OPVC structure, highlighting that vacuum level alignment cannot reliably be used to estimate the electronic properties for device design. Particularly the effective electrode work function values (after contact formation with the conjugated polymers) differ significantly from those of the pristine electrode materials. Chemical reactions between PEDT:PSS and P3HT on the one hand and Ca and PFTBTT on the other hand are identified as cause for the measured interface dipoles. The vacuum level shift between P3HT and PFTBTT is related to mutual energy level pinning at gap states. Annealing induced morphological changes at the P3HT/PFTBTT interface increased the efficiency of OPVCs, while the electronic structure was not affected by thermal treatment.

• S.T. Turner, P. Pingel, R. Steyrleuthner, E.J.W. Crossland, S. Ludwigs & D. Neher, “Quantitative Analysis of Bulk Heterojunction Films Using Linear Absorption Spectroscopy and Solar Cell Performance”, Advanced Functional Materials21, 4640 (2011) DOI

  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.

• J.C. Blakesley, M. Schubert, R. Steyrleuthner, Z. Chen, A. Facchetti & D. Neher, “Time-of-flight measurements and vertical transport in a high electron-mobility polymer”, Applied Physics Letters99, 183310 (2011) DOI • PDF

  We investigate charge transport in a high-electron mobility polymer, poly(N,N-bis 2-octyldodecyl-naphthalene-1,4,5,8-bis dicarboximide-2,6-diyl-alt-5,5-2,2-bithiophene) [P(NDI2OD-T2), Polyera ActivInk™ N2200]. Time-of-flight measurements reveal electron mobilities approaching those measured in field-effect transistors, the highest ever recorded in a conjugated polymer using this technique. The modest temperature dependence and weak dispersion of the transients indicate low energetic disorder in this material. Steady-state electron-only current measurements reveal a barrier to injection of about 300 meV. We propose that this barrier is located within the P(NDI2OD-T2) film and arises from molecular orientation effects.

• S.A. Bagnich, T. Unger, F. Jaiser, D. Neher, M.W. Thesen, H. Krueger, “Efficient green electrophosphorescence based on ambipolar nonconjugated polymers: Evaluation of transport and emission properties”, Journal of Applied Physics110, 033724 (2011) DOI • PDF

  New materials for polymer organic light-emitting diodes based on a polymer matrix doped with phosphorescent dyes are presented. The matrix system is based on a polystyrene backbone bearing either electron or hole transporting units at the 4-position of each repeat unit. Random copolymers and polymer blend systems of the homopolymers are prepared, both with 62 wt.% electron transporting and 38 wt.% hole transporting moieties. Adding a green electrophosphorescent dye to the polymer matrix leads to efficient electroluminescence with a maximum current efficiency of 35 cd/A and a maximum external quantum efficiency of up to 10%. The mobilities of electrons and holes in the dye-doped copolymer, as measured by transient electroluminescence, are around 5×10⁻⁵ and 5×10⁻⁶ cm²/Vs, respectively, while the blend of the two homopolymers exhibits slightly lower mobilities of both types of carriers. Despite the pronounced imbalance of charge transport, the device performance is almost entirely limited by the phosphorescence efficiency of the dye, implying balanced flow of holes and electrons into the active region. Also, devices made with either the copolymer or the blend yielded very similar device efficiencies, despite the noticeable difference in electron and hole mobility. It is proposed that electrons are efficiently blocked at the interlayer and that the so-formed space charge assists the balanced injection of holes.

• J.C. Blakesley, D. Neher, “Relationship between energetic disorder and open-circuit voltage in bulk heterojunction organic solar cells”, Physical Review B84, 075210 (2011) DOI • PDF

  We simulate organic bulk heterojunction solar cells. The effects of energetic disorder are incorporated through a Gaussian or exponential model of density of states. Analytical models of open-circuit voltage (V_OC) are derived from the splitting of quasi-Fermi potentials. Their predictions are backed up by more complex numerical device simulations including effects such as carrier-density–dependent charge-carrier mobilities. It is predicted that the V_OC depends on: (1) the donor-acceptor energy gap; (2) charge-carrier recombination rates; (3) illumination intensity; (4) the contact work functions (if not in the pinning regime); and (5) the amount of energetic disorder. A large degree of energetic disorder, or a high density of traps, is found to cause significant reductions in V_OC. This can explain why V_OC is often less than expected in real devices. Energetic disorder also explains the nonideal temperature and intensity dependence of V_OC and the superbimolecular recombination rates observed in many real bulk heterojunction solar cells.

• J. Rivnay, R. Steyrleuthner, L.H. Jimison, A. Casadei, Z. Chen, M.F. Toney, A. Facchetti, D. Neher & A. Salleo, “Drastic Control of Texture in a High Performance n-Type Polymeric Semiconductor and Implications for Charge Transport”, Macromolecules44, 5246 (2011) DOI

  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-diyl]-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.

• J.M. Ilnytskyi, D. Neher & M. Saphiannikova, “Opposite photo-induced deformations in azobenzene-containing polymers with different molecular architecture: Molecular dynamics study”, Journal of Chemical Physics135, 044901 (2011) DOI • PDF

  Photo-induced deformations in azobenzene-containing polymers (azo-polymers) are central to a number of applications, such as optical storage and fabrication of diffractive elements. The microscopic nature of the underlying opto-mechanical coupling is yet not clear. In this study, we address the experimental finding that the scenario of the effects depends on molecular architecture of the used azo-polymer. Typically, opposite deformations in respect to the direction of light polarization are observed for liquid crystalline and amorphous azo-polymers. In this study, we undertake molecular dynamics simulations of two different models that mimic these two types of azo-polymers. We employ hybrid force field modeling and consider only trans-isomers of azobenzene, represented as Gay-Berne sites. The effect of illumination on the orientation of the chromophores is considered on the level of orientational hole burning and emphasis is given to the resulting deformation of the polymer matrix. We reproduce deformations of opposite sign for the two models being considered here and discuss the relevant microscopic mechanisms in both cases.

• I. Lange, J.C. Blakesley, J. Frisch, A. Vollmer, N. Koch, D. Neher, “Band Bending in Conjugated Polymer Layers”, Physical Review Letters106, 216402 (2011) DOI • PDF • Supporting Information

  We use the Kelvin probe method to study the energy-level alignment of four conjugated polymers deposited on various electrodes. Band bending is observed in all polymers when the substrate work function exceeds critical values. Through modeling, we show that the band bending is explained by charge transfer from the electrodes into a small density of states that extends several hundred meV into the band gap. The energetic spread of these states is correlated with charge-carrier mobilities, suggesting that the same states also govern charge transport in the bulk of these polymers.

• J. Kniepert, M. Schubert, J.C. Blakesley, D. Neher, “Photogeneration and Recombination in P3HT/PCBM Solar Cells Probed by Time-Delayed Collection Field Experiments”, The Journal of Physical Chemistry Letters2, 700 (2011) DOI

  Time-delayed collection field (TDCF) experiments are performed on bulk heterojunction solar cells comprised of a blend of poly(3-hexylthiophene) and [6,6]-phenyl C₇₁ butyric acid methyl ester. TDCF is analogous to a pump−probe experiment using optical excitation and an electrical probe with a resolution of <100 ns. The number of free charge carriers extracted after a short delay is found to be independent of the electric field during illumination. Also, experiments performed with a variable delay between the optical excitation and the electrical probe do not reveal any evidence for the generation of charge via field-assisted dissociation of bound long-lived polaron pairs. Photocurrent transients are well fitted by computational drift diffusion simulations with only direct generation of free charge carriers. With increasing delay times between pump and probe, two loss mechanisms are identified; first, charge-carriers are swept out of the device by the internal electric field, and second, bimolecular recombination of the remaining carriers takes place with a reduced recombination coefficient.

• S. Kuehn, P. Pingel, M. Breusing, Th. Fischer, J. Stumpe, D. Neher, Th. Elsaesser, “High-Resolution Near-Field Optical Investigation of Crystalline Domains in Oligomeric PQT-12 Thin Films”, Advanced Functional Materials21, 860 (2011) DOI

  The structure and morphology on different length scales dictate both the electrical and optical properties of organic semiconductor thin films. Using a combination of spectroscopic methods, including scanning near-field optical microscopy, we study the domain structure and packing quality of highly crystalline thin films of oligomeric PQT-12 with 100 nanometer spatial resolution. The pronounced optical anisotropy of these layers measured by polarized light microscopy facilitates the identification of regions with uniform molecular orientation. We find that a hierarchical order on three different length scales exists in these layers, made up of distinct well-ordered dichroic areas at the ten-micrometer-scale, which are sub-divided into domains with different molecular in-plane orientation. These serve as a template for the formation of smaller needle-like crystallites at the layer surface. A high degree of crystalline order is believed to be the cause of the rather high field-effect mobility of these layers of 10⁻³ cm² V⁻¹ s⁻¹, whereas it is limited by the presence of domain boundaries at macroscopic distances.

• P. Pingel, A. Zen, R.D. Abellón, F.C. Grozema, L.D.A. Siebbeles, and D. Neher, “Temperature-Resolved Local and Macroscopic Charge Carrier Transport in Thin P3HT Layers”, Advanced Functional Materials 20, 2286 (2010) DOI

  Previous investigations of the field-effect mobility in poly(3-hexylthiophene) (P3HT) layers revealed a strong dependence on molecular weight (MW), which was shown to be closely related to layer morphology. Here, charge carrier mobilities of two P3HT MW fractions (medium-MW: M_n = 7 200 g/mol; high-MW: M_n = 27 000 g/mol) are probed as a function of temperature at a local and a macroscopic length scale, using pulseradiolysis time-resolved microwave conductivity (PR-TRMC) and organic field-effect transistor measurements, respectively. In contrast to the macroscopic transport properties, the local intra-grain mobility depends only weakly on MW (being in the order of 0.01 cm²/(Vs)) and being thermally activated below the melting temperature for both fractions. The striking differences of charge transport at both length scales are related to the heterogeneity of the layer morphology. The quantitative analysis of temperature-dependent UV/Vis absorption spectra according to a model of F. C. Spano reveals that a substantial amount of disordered material is present in these P3HT layers. Moreover, the analysis predicts that aggregates in medium-MW P3HT undergo a ‘‘pre-melting’’ significantly below the actual melting temperature. The results suggest that macroscopic charge transport in samples of short-chain P3HT is strongly inhibited by the presence of disordered domains, while in high-MW P3HT the low-mobility disordered zones are bridged via inter-crystalline molecular connections.

• R. Steyrleuthner, M. Schubert, F. Jaiser, J.C. Blakesley, Z. Chen, A. Facchetti, D. Neher, “Bulk Electron Transport and Charge Injection in a High Mobility n-Type Semiconducting Polymer”, Advanced Materials 22, 2799 (2010) DOI

  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  ≈5×10^-3 cm²/Vs are obtained. The analysis of the electron currents suggests the presence of an injection barrier for all conventionally used low workfunction cathodes.

• S. Inal, M. Schubert, A. Sellinger, D. Neher, “The Relationship between the Electric Field-Induced Dissociation of Charge Transfer Excitons and the Photocurrent in Small Molecular/Polymeric Solar Cells”, The Journal of Physical Chemistry Letters1, 982 (2010) DOI

  A bulk heterojunction system consisting of a soluble poly(p-phenylenevinylene) donor and a small molecular electron acceptor based on Vinazene (2-vinyl-4,5-dicyanoimidazole) has been investigated with respect to the correlation between field-induced emission quenching and free charge carrier formation. Transient and steady-state emission properties measured at different voltages indicate that emissive charge transfer (CT) excitons formed at the heterojunction are prone to direct field-induced dissociation. However, the split-up of these CT excitons cannot fully account for the photocurrents observed on the very same devices. It is proposed that the formation of free carriers involves a nonemissive precursor and that the recombination of this precursor does not proceed via the formation of CT excitons.

• S. Bange, M. Schubert, D. Neher, “Charge mobility determination by current extraction under linear increasing voltages: Case of nonequilibrium charges and field-dependent mobilities”, Physical Review B 81, 035209 (2010) DOI • PDF

  The method of current extraction under linear increasing voltages (CELIV) allows for the simultaneous determination of charge mobilities and charge densities directly in thin-film geometries as used in organic photovoltaic (OPV) cells. It has been specifically applied to investigate the interrelation of microstructure and charge-transport properties in such systems. Numerical and analytical calculations presented in this work show that the evaluation of CELIV transients with the commonly used analysis scheme is error prone once charge recombination and, possibly, field-dependent charge mobilities are taken into account. The most important effects are an apparent time dependence of charge mobilities and errors in the determined field dependencies. Our results implicate that reports on time-dependent mobility relaxation in OPV materials obtained by the CELIV technique should be carefully revisited and confirmed by other measurement methods.

2005 – 2009

2000 – 2004

up to 1999