@article{LangeReiterKniepertetal.2015, author = {Lange, Ilja and Reiter, Sina and Kniepert, Juliane and Piersimoni, Fortunato and Paetzel, Michael and Hildebrandt, Jana and Brenner, Thomas J. K. and Hecht, Stefan and Neher, Dieter}, title = {Zinc oxide modified with benzylphosphonic acids as transparent electrodes in regular and inverted organic solar cell structures}, series = {Applied physics letters}, volume = {106}, journal = {Applied physics letters}, number = {11}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.4916182}, pages = {5}, year = {2015}, abstract = {An approach is presented to modify the work function of solution-processed sol-gel derived zinc oxide (ZnO) over an exceptionally wide range of more than 2.3 eV. This approach relies on the formation of dense and homogeneous self-assembled monolayers based on phosphonic acids with different dipole moments. This allows us to apply ZnO as charge selective bottom electrodes in either regular or inverted solar cell structures, using poly(3-hexylthiophene): phenyl-C71-butyric acid methyl ester as the active layer. These devices compete with or even surpass the performance of the reference on indium tin oxide/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Our findings highlight the potential of properly modified ZnO as electron or hole extracting electrodes in hybrid optoelectronic devices. (C) 2015 AIP Publishing LLC.}, language = {en} } @article{SunSandbergNeheretal.2022, author = {Sun, Bowen and Sandberg, Oskar and Neher, Dieter and Armin, Ardalan and Shoaee, Safa}, title = {Wave optics of differential absorption spectroscopy in thick-junction organic solar cells}, series = {Physical review applied / The American Physical Society}, volume = {17}, journal = {Physical review applied / The American Physical Society}, number = {5}, publisher = {American Physical Society}, address = {College Park}, issn = {2331-7019}, doi = {10.1103/PhysRevApplied.17.054016}, pages = {12}, year = {2022}, abstract = {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.}, language = {en} } @article{StolterfohtLeCorreFeuersteinetal.2019, author = {Stolterfoht, Martin and Le Corre, Vincent M. and Feuerstein, Markus and Caprioglio, Pietro and Koster, Lambert Jan Anton and Neher, Dieter}, title = {Voltage-Dependent Photoluminescence and How It Correlates with the Fill Factor and Open-Circuit Voltage in Perovskite Solar Cells}, series = {Acs energy letters}, volume = {4}, journal = {Acs energy letters}, number = {12}, publisher = {American Chemical Society}, address = {Washington}, issn = {2380-8195}, doi = {10.1021/acsenergylett.9b02262}, pages = {2887 -- 2892}, year = {2019}, abstract = {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.}, language = {en} } @article{StolterfohtWolffMarquezetal.2018, author = {Stolterfoht, Martin and Wolff, Christian Michael and Marquez, Jose A. and Zhang, Shanshan and Hages, Charles J. and Rothhardt, Daniel and Albrecht, Steve and Burn, Paul L. and Meredith, Paul and Unold, Thomas and Neher, Dieter}, title = {Visualization and suppression of interfacial recombination for high-efficiency large-area pin perovskite solar cells}, series = {Nature Energy}, volume = {3}, journal = {Nature Energy}, number = {10}, publisher = {Nature Publ. Group}, address = {London}, issn = {2058-7546}, doi = {10.1038/s41560-018-0219-8}, pages = {847 -- 854}, year = {2018}, abstract = {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\%).}, language = {en} } @article{XuBrennerChenetal.2014, author = {Xu, Jingsan and Brenner, Thomas J. K. and Chen, Zupeng and Neher, Dieter and Antonietti, Markus and Shalom, Menny}, title = {Upconversion-agent induced improvement of g-C3N4 photocatalyst under visible light}, series = {ACS applied materials \& interfaces}, volume = {6}, journal = {ACS applied materials \& interfaces}, number = {19}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/am5051263}, pages = {16481 -- 16486}, year = {2014}, abstract = {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.}, language = {en} } @article{ZuWolffRalaiarisoaetal.2019, author = {Zu, Fengshuo and Wolff, Christian Michael and Ralaiarisoa, Maryline and Amsalem, Patrick and Neher, Dieter and Koch, Norbert}, title = {Unraveling the Electronic Properties of Lead Halide Perovskites with Surface Photovoltage in Photoemission Studies}, series = {ACS applied materials \& interfaces}, volume = {11}, journal = {ACS applied materials \& interfaces}, number = {24}, publisher = {American Chemical Society}, address = {Washington}, issn = {1944-8244}, doi = {10.1021/acsami.9b05293}, pages = {21578 -- 21583}, year = {2019}, abstract = {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.}, language = {en} } @article{PingelZenNeheretal.2009, author = {Pingel, Patrick and Zen, Achmad and Neher, Dieter and Lieberwirth, Ingo and Wegner, Gerhard and Allard, Sybille and Scherf, Ullrich}, title = {Unexpectedly high field-effect mobility of a soluble, low molecular weight oligoquaterthiophene fraction with low polydispersity}, issn = {0947-8396}, doi = {10.1007/s00339-008-4994-0}, year = {2009}, abstract = {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.}, language = {en} } @article{PerdigonToroLeQuangPhuongElleretal.2022, author = {Perdig{\´o}n-Toro, Lorena and Le Quang Phuong, and Eller, Fabian and Freychet, Guillaume and Saglamkaya, Elifnaz and Khan, Jafar and Wei, Qingya and Zeiske, Stefan and Kroh, Daniel and Wedler, Stefan and Koehler, Anna and Armin, Ardalan and Laquai, Frederic and Herzig, Eva M. and Zou, Yingping and Shoaee, Safa and Neher, Dieter}, title = {Understanding the role of order in Y-series non-fullerene solar cells to realize high open-circuit voltages}, series = {Advanced energy materials}, volume = {12}, journal = {Advanced energy materials}, number = {12}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.202103422}, pages = {13}, year = {2022}, abstract = {Non-fullerene acceptors (NFAs) as used in state-of-the-art organic solar cells feature highly crystalline layers that go along with low energetic disorder. Here, the crucial role of energetic disorder in blends of the donor polymer PM6 with two Y-series NFAs, Y6, and N4 is studied. By performing temperature-dependent charge transport and recombination studies, a consistent picture of the shape of the density of state distributions for free charges in the two blends is developed, allowing an analytical description of the dependence of the open-circuit voltage V-OC on temperature and illumination intensity. Disorder is found to influence the value of the V-OC at room temperature, but also its progression with temperature. Here, the PM6:Y6 blend benefits substantially from its narrower state distributions. The analysis also shows that the energy of the equilibrated free charge population is well below the energy of the NFA singlet excitons for both blends and possibly below the energy of the populated charge transfer manifold, indicating a down-hill driving force for free charge formation. It is concluded that energetic disorder of charge-separated states has to be considered in the analysis of the photovoltaic properties, even for the more ordered PM6:Y6 blend.}, language = {en} } @article{WarbyZuZeiskeetal.2022, author = {Warby, Jonathan and Zu, Fengshuo and Zeiske, Stefan and Gutierrez-Partida, Emilio and Frohloff, Lennart and Kahmann, Simon and Frohna, Kyle and Mosconi, Edoardo and Radicchi, Eros and Lang, Felix and Shah, Sahil and Pena-Camargo, Francisco and Hempel, Hannes and Unold, Thomas and Koch, Norbert and Armin, Ardalan and De Angelis, Filippo and Stranks, Samuel D. and Neher, Dieter and Stolterfoht, Martin}, title = {Understanding performance limiting interfacial recombination in pin Perovskite solar cells}, series = {Advanced energy materials}, volume = {12}, journal = {Advanced energy materials}, number = {12}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.202103567}, pages = {10}, year = {2022}, abstract = {Perovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto-electronic properties and their successful integration into multijunction cells. However, the performance of single- and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/C-60 interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first-principle numerical simulations. It is found that the most significant contribution to the total C-60-induced recombination loss occurs within the first monolayer of C-60, rather than in the bulk of C-60 or at the perovskite surface. The experiments show that the C-60 molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of C-60, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.}, language = {en} } @article{LangeReiterPaetzeletal.2014, author = {Lange, Ilja and Reiter, Sina and Paetzel, Michael and Zykov, Anton and Nefedov, Alexei and Hildebrandt, Jana and Hecht, Stefan and Kowarik, Stefan and Woell, Christof and Heimel, Georg and Neher, Dieter}, title = {Tuning the work function of polar zinc oxide surfaces using modified phosphonic acid self-assembled monolayers}, series = {Advanced functional materials}, volume = {24}, journal = {Advanced functional materials}, number = {44}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1616-301X}, doi = {10.1002/adfm.201401493}, pages = {7014 -- 7024}, year = {2014}, abstract = {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.}, language = {en} } @article{SchubertFrischAllardetal.2017, author = {Schubert, Marcel and Frisch, Johannes and Allard, Sybille and Preis, Eduard and Scherf, Ullrich and Koch, Norbert and Neher, Dieter}, title = {Tuning side chain and main chain order in a prototypical donor-acceptor copolymer}, series = {Elementary Processes in Organic Photovoltaics}, volume = {272}, journal = {Elementary Processes in Organic Photovoltaics}, publisher = {Springer}, address = {Berlin}, isbn = {978-3-319-28338-8}, issn = {0065-3195}, doi = {10.1007/978-3-319-28338-8_10}, pages = {243 -- 265}, year = {2017}, abstract = {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.}, language = {en} } @article{BlakesleySchubertSteyrleuthneretal.2011, author = {Blakesley, James C. and Schubert, Marcel and Steyrleuthner, Robert and Chen, Zhihua and Facchetti, Antonio and Neher, Dieter}, title = {Time-of-flight measurements and vertical transport in a high electron-mobility polymer}, series = {Applied physics letters}, volume = {99}, journal = {Applied physics letters}, number = {18}, publisher = {American Institute of Physics}, address = {Melville}, issn = {0003-6951}, doi = {10.1063/1.3657827}, pages = {3}, year = {2011}, abstract = {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 (TM) 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.}, language = {en} } @article{SaphiannikovaNeher2005, author = {Saphiannikova, Marina and Neher, Dieter}, title = {Thermodynamic theory of light-induced material transport in amorphous azobenzene polymer films}, issn = {1520-6106}, year = {2005}, abstract = {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}, language = {en} } @article{StolterfohtArminPhilippaetal.2016, author = {Stolterfoht, Martin and Armin, Ardalan and Philippa, Bronson and Neher, Dieter}, title = {The Role of Space Charge Effects on the Competition between Recombination and Extraction in Solar Cells with Low-Mobility Photoactive Layers}, series = {The journal of physical chemistry letters}, volume = {7}, journal = {The journal of physical chemistry letters}, publisher = {American Chemical Society}, address = {Washington}, issn = {1948-7185}, doi = {10.1021/acs.jpclett.6b02106}, pages = {4716 -- 4721}, year = {2016}, abstract = {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.}, language = {en} } @article{SteyrleuthnerDiPietroCollinsetal.2014, author = {Steyrleuthner, Robert and Di Pietro, Riccardo and Collins, Brian A. and Polzer, Frank and Himmelberger, Scott and Schubert, Marcel and Chen, Zhihua and Zhang, Shiming and Salleo, Alberto and Ade, Harald W. and Facchetti, Antonio and Neher, Dieter}, title = {The Role of Regioregularity, Crystallinity, and Chain Orientation on Electron Transport in a High-Mobility n-Type Copolymer}, series = {Journal of the American Chemical Society}, volume = {136}, journal = {Journal of the American Chemical Society}, number = {11}, publisher = {American Chemical Society}, address = {Washington}, issn = {0002-7863}, doi = {10.1021/ja4118736}, pages = {4245 -- 4256}, year = {2014}, language = {en} } @misc{ShoaeeStolterfohtNeher2018, author = {Shoaee, Safa and Stolterfoht, Martin and Neher, Dieter}, title = {The Role of Mobility on Charge Generation, Recombination, and Extraction in Polymer-Based Solar Cells}, series = {dvanced energy materials}, volume = {8}, journal = {dvanced energy materials}, number = {28}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {1614-6832}, doi = {10.1002/aenm.201703355}, pages = {20}, year = {2018}, abstract = {Organic semiconductors are of great interest for a broad range of optoelectronic applications due to their solution processability, chemical tunability, highly scalable fabrication, and mechanical flexibility. In contrast to traditional inorganic semiconductors, organic semiconductors are intrinsically disordered systems and therefore exhibit much lower charge carrier mobilities-the Achilles heel of organic photovoltaic cells. In this progress review, the authors discuss recent important developments on the impact of charge carrier mobility on the charge transfer state dissociation, and the interplay of free charge extraction and recombination. By comparing the mobilities on different timescales obtained by different techniques, the authors highlight the dispersive nature of these materials and how this reflects on the key processes defining the efficiency of organic photovoltaics.}, language = {en} } @article{ZhangHosseiniGunderetal.2019, author = {Zhang, Shanshan and Hosseini, Seyed Mehrdad and Gunder, Rene and Petsiuk, Andrei and Caprioglio, Pietro and Wolff, Christian Michael and Shoaee, Safa and Meredith, Paul and Schorr, Susan and Unold, Thomas and Burn, Paul L. and Neher, Dieter and Stolterfoht, Martin}, title = {The Role of Bulk and Interface Recombination in High-Efficiency Low-Dimensional Perovskite Solar Cells}, series = {Advanced materials}, volume = {31}, journal = {Advanced materials}, number = {30}, publisher = {Wiley-VCH}, address = {Weinheim}, issn = {0935-9648}, doi = {10.1002/adma.201901090}, pages = {11}, year = {2019}, abstract = {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.}, language = {en} } @article{MansourLungwitzSchultzetal.2020, author = {Mansour, Ahmed E. and Lungwitz, Dominique and Schultz, Thorsten and Arvind, Malavika and Valencia, Ana M. and Cocchi, Caterina and Opitz, Andreas and Neher, Dieter and Koch, Norbert}, title = {The optical signatures of molecular-doping induced polarons in poly(3-hexylthiophene-2,5-diyl)}, series = {Journal of materials chemistry : C, Materials for optical and electronic devices}, volume = {8}, journal = {Journal of materials chemistry : C, Materials for optical and electronic devices}, number = {8}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {2050-7526}, doi = {10.1039/c9tc06509a}, pages = {2870 -- 2879}, year = {2020}, abstract = {Optical absorption spectroscopy is a key method to investigate doped conjugated polymers and to characterize the doping-induced charge carriers, i.e., polarons. For prototypical poly(3-hexylthiophene-2,5-diyl) (P3HT), the absorption intensity of molecular dopant induced polarons is widely used to estimate the carrier density and the doping efficiency, i.e., the number of polarons formed per dopant molecule. However, the dependence of the polaron-related absorption features on the structure of doped P3HT, being either aggregates or separated individual chains, is not comprehensively understood in contrast to the optical absorption features of neutral P3HT. In this work, we unambiguously differentiate the optical signatures of polarons on individual P3HT chains and aggregates in solution, notably the latter exhibiting the same shape as aggregates in solid thin films. This is enabled by employing tris(pentafluorophenyl)borane (BCF) as dopant, as this dopant forms only ion pairs with P3HT and no charge transfer complexes, and BCF and its anion have no absorption in the spectral region of P3HT polarons. Polarons on individual chains exhibit absorption peaks at 1.5 eV and 0.6 eV, whereas in aggregates the high-energy peak is split into a doublet 1.3 eV and 1.65 eV, and the low-energy peak is shifted below 0.5 eV. The dependence of the fraction of solvated individual chains versus aggregates on absolute solution concentration, dopant concentration, and temperature is elucidated, and we find that aggregates predominate in solution under commonly used processing conditions. Aggregates in BCF-doped P3HT solution can be effectively removed upon simple filtering. From varying the filter pore size (down to 200 nm) and thin film morphology characterization with scanning force microscopy we reveal the aggregates' size dependence on solution absolute concentration and dopant concentration. Furthermore, X-ray photoelectron spectroscopy shows that the dopant loading in aggregates is higher than for individual P3HT chains. The results of this study help understanding the impact of solution pre-aggregation on thin film properties of molecularly doped P3HT, and highlight the importance of considering such aggregation for other doped conjugated polymers in general.}, language = {en} } @article{StolterfohtCaprioglioWolffetal.2019, author = {Stolterfoht, Martin and Caprioglio, Pietro and Wolff, Christian Michael and Marquez, Jose A. and Nordmann, Joleik and Zhang, Shanshan and Rothhardt, Daniel and H{\"o}rmann, Ulrich and Amir, Yohai and Redinger, Alex and Kegelmann, Lukas and Zu, Fengshuo and Albrecht, Steve and Koch, Norbert and Kirchartz, Thomas and Saliba, Michael and Unold, Thomas and Neher, Dieter}, title = {The impact of energy alignment and interfacial recombination on the internal and external open-circuit voltage of perovskite solar cells}, series = {Energy \& environmental science}, volume = {12}, journal = {Energy \& environmental science}, number = {9}, publisher = {Royal Society of Chemistry}, address = {Cambridge}, issn = {1754-5692}, doi = {10.1039/c9ee02020a}, pages = {2778 -- 2788}, year = {2019}, abstract = {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.}, language = {en} } @article{SainovaFujikawaScherfetal.1999, author = {Sainova, Dessislava and Fujikawa, H. and Scherf, Ullrich and Neher, Dieter}, title = {The effect of hole traps on the performance of single layer polymer light emitting diodes}, year = {1999}, language = {en} }