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Z. Chen, A. Savateev, S. Pronkin, V. Papaefthimiou, C. Wolff, M. G. Willinger, E. Willinger, D. Neher, M. Antonietti, D. Dontsova, “‘The Easier the Better’ Preparation of Efficient Photocatalysts—Metastable Poly(heptazine imide) Salts”, Advanced Materials (2017), DOI: 10.1002/adma.201700555
Cost-efficient, visible-light-driven hydrogen production from water is an attractive potential source of clean, sustainable fuel. Here, it is shown that thermal solid state reactions of traditional carbon nitride precursors (cyanamide, melamine) with NaCl, KCl, or CsCl are a cheap and straightforward way to prepare poly(heptazine imide) alkali metal salts, whose thermodynamic stability decreases upon the increase of the metal atom size. The chemical structure of the prepared salts is confirmed by the results of X-ray photoelectron and infrared spectroscopies, powder X-ray diffraction and electron microscopy studies, and, in the case of sodium poly(heptazine imide), additionally by atomic pair distribution function analysis and 2D powder X-ray diffraction pattern simulations. In contrast, reactions with LiCl yield thermodynamically stable poly(triazine imides). Owing to the metastability and high structural order, the obtained heptazine imide salts are found to be highly active photocatalysts in Rhodamine B and 4-chlorophenol degradation, and Pt-assisted sacrificial water reduction reactions under visible light irradiation. The measured hydrogen evolution rates are up to four times higher than those provided by a benchmark photocatalyst, mesoporous graphitic carbon nitride. Moreover, the products are able to photocatalytically reduce water with considerable reaction rates, even when glycerol is used as a sacrificial hole scavenger.
N. A. Ran, S. Roland, J. A. Love, V. Savikhin, C. J. Takacs, Y.-T. Fu, H. Li, V. Coropceanu, X. Liu, J.-L. Brédas, G. C. Bazan, M. F. Toney, D. Neher, T.-Q. Nguyen, “Impact of interfacial molecular orientation on radiative recombination and charge generation efficiency”, Nature Communications 8, 79 (2017), DOI: 10.1038/s41467-017-00107-4
A long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics—however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting in larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.
C. M. Wolff, F. Zu, A. Paulke, L. Perdigón-Toro, N. Koch, D. Neher, “Reduced Interface-Mediated Recombination for High Open-Circuit Voltages in CH3NH3PbI3 Solar Cells”, Advanced Materials 29, 1700159 (2017), DOI: 10.1002/adma.201700159
Perovskite solar cells with all-organic transport layers exhibit efficiencies rivaling their counterparts that employ inorganic transport layers, while avoiding high-temperature processing. Herein, it is investigated how the choice of the fullerene derivative employed in the electron-transporting layer of inverted perovskite cells affects the open-circuit voltage (VOC). It is shown that nonradiative recombination mediated by the electron-transporting layer is the limiting factor for the VOC in the cells. By inserting an ultrathin layer of an insulating polymer between the active CH3NH3PbI3 perovskite and the fullerene, an external radiative efficiency of up to 0.3%, a VOC as high as 1.16 V, and a power conversion efficiency of 19.4% are realized. The results show that the reduction of nonradiative recombination due to charge-blocking at the perovskite/organic interface is more important than proper level alignment in the search for ideal selective contacts toward high VOC and efficiency.
J. Benduhn, K. Tvingstedt, F. Piersimoni, S. Ullbrich, Y. Fan, M. Tropiano, K. A. McGarry, O. Zeika, M. K. Riede, C. J. Douglas, S. Barlow, S. R. Marder, D. Neher, D. Spoltore & K. Vandewal, “Intrinsic non-radiative voltage losses in fullerene-based organic solar cells”, Nature Energy 2, 17053 (2017), DOI: 10.1038/nenergy.2017.53
Organic solar cells demonstrate external quantum efficiencies and fill factors approaching those of conventional photovoltaic technologies. However, as compared with the optical gap of the absorber materials, their open-circuit voltage is much lower, largely due to the presence of significant non-radiative recombination. Here, we study a large data set of published and new material combinations and find that non-radiative voltage losses decrease with increasing charge-transfer-state energies. This observation is explained by considering non-radiative charge-transfer-state decay as electron transfer in the Marcus inverted regime, being facilitated by a common skeletal molecular vibrational mode. Our results suggest an intrinsic link between non-radiative voltage losses and electron-vibration coupling, indicating that these losses are unavoidable. Accordingly, the theoretical upper limit for the power conversion efficiency of single-junction organic solar cells would be reduced to about 25.5% and the optimal optical gap increases to 1.45–1.65 eV, that is, 0.2–0.3 eV higher than for technologies with minimized non-radiative voltage losses.
L. Kegelmann, C. M. Wolff, C. A. Omondi, F. Lang, E. L. Unger, L. Korte, T. Dittrich, D. Neher, B. Rech, S. Albrecht, “It takes two to tango – double-layer selective contacts in perovskite solar cells for improved device performance and reduced hysteresis”, ACS Applied Materials & Interfaces 9, 17245-17255 (2017), DOI: 10.1021/acsami.7b00900
Solar cells made from inorganic-organic perovskites gradually approach market requirements as efficiency and stability improved tremendously in recent years. Planar low-temperature processed perovskite solar cells are advantageous for a possible large-scale production but are more prone to exhibit photocurrent hysteresis, especially in the regular n-i-p structure. Here, a systematic characterization of different electron selective contacts with a variety of chemical and electrical properties in planar n-i-p devices processed below 180 °C is presented. The inorganic metal oxides TiO2 and SnO2, the organic fullerene derivatives C60, PCBM and ICMA as well as double-layers with a metal oxide/PCBM structure are used as electron transport materials (ETMs). Perovskite layers deposited atop the different ETMs with the herein applied fabrication method show a similar morphology according to scanning electron microscopy. Further, surface photovoltage spectroscopy measurements indicate comparable perovskite absorber qualities on all ETMs except TiO2 showing a more prominent influence of defect states. Transient photoluminescence studies together with current-voltage scans over a broad range of scan speeds reveal faster charge extraction, less pronounced hysteresis effects and higher efficiencies for devices with fullerene compared to metal oxide ETMs. Beyond this, only double-layer ETM structures substantially diminish hysteresis effects for all performed scan speeds and strongly enhance the power conversion efficiency up to a champion stabilized value of 18.0 %. The results indicate reduced recombination losses for a double layer TiO2/PCBM contact design: First a reduction of shunt paths through the fullerene to the ITO layer. Second, an improved hole blocking by the wide band-gap metal oxide. Third, decreased transport losses due to an energetically more favorable contact as implied by photoelectron spectroscopy measurements. The herein demonstrated improvements of multi-layer selective contacts may serve as a general design guideline for perovskite solar cells.
S. Roland, L. Yan, Q. Zhang, X. Jiao, A. Hunt, M. Ghasemi, H. Ade, W. You, D. Neher, “Charge Generation and Mobility-Limited Performance of Bulk Heterojunction Solar Cells with a Higher Adduct Fullerene”, The Journal of Physical Chemistry C 121, 10305-10316 (2017), DOI: 10.1021/acs.jpcc.7b02288
Alternative electron acceptors are being actively explored in order to advance the development of bulk-heterojunction (BHJ) organic solar cells (OSCs). The indene–C60 bisadduct (ICBA) has been regarded as a promising candidate, as it provides high open-circuit voltage in BHJ solar cells; however, the photovoltaic performance of such ICBA-based devices is often inferior when compared to cells with the omnipresent PCBM electron acceptor. Here, by pairing the high performance polymer (FTAZ) as the donor with either PCBM or ICBA as the acceptor, we explore the physical mechanism behind the reduced performance of the ICBA-based device. Time delayed collection field (TDCF) experiments reveal reduced, yet field-independent free charge generation in the FTAZ:ICBA system, explaining the overall lower photocurrent in its cells. Through the analysis of the photoluminescence, photogeneration, and electroluminescence, we find that the lower generation efficiency is neither caused by inefficient exciton splitting, nor do we find evidence for significant energy back-transfer from the CT state to singlet excitons. In fact, the increase in open circuit voltage when replacing PCBM by ICBA is entirely caused by the increase in the CT energy, related to the shift in the LUMO energy, while changes in the radiative and nonradiative recombination losses are nearly absent. On the other hand, space charge limited current (SCLC) and bias-assisted charge extraction (BACE) measurements consistently reveal a severely lower electron mobilitiy in the FTAZ:ICBA blend. Studies of the blends with resonant soft X-ray scattering (R-SoXS), grazing incident wide-angle X-ray scattering (GIWAXS), and scanning transmission X-ray microscopy (STXM) reveal very little differences in the mesoscopic morphology but significantly less nanoscale molecular ordering of the fullerene domains in the ICBA based blends, which we propose as the main cause for the lower generation efficiency and smaller electron mobility. Calculations of the JV curves with an analytical model, using measured values, show good agreement with the experimentally determined JV characteristics, proving that these devices suffer from slow carrier extraction, resulting in significant bimolecular recombination losses. Therefore, this study highlights the importance of high charge carrier mobility for newly synthesized acceptor materials, in addition to having suitable energy levels.
M. Jošt, S. Albrecht, L. Kegelmann, C. M. Wolff, F. Lang, B. Lipovšek, J. Krč, L. Korte, D. Neher, B. Rech, M. Topič, “Efficient Light Management by Textured Nanoimprinted Layers for Perovskite Solar Cells”, ACS Photonics 4, 1232-1239 (2017), DOI: 10.1021/acsphotonics.7b00138
Inorganic–organic perovskites like methylammonium-lead-iodide have proven to be an effective class of materials for fabricating efficient solar cells. To improve their performance, light management techniques using textured surfaces, similar to those used in established solar cell technologies, should be considered. Here, we apply a light management foil created by UV nanoimprint lithography on the glass side of an inverted (p-i-n) perovskite solar cell with 16.3% efficiency. The obtained 1 mA/cm² increase in the short-circuit current density translates to a relative improvement in cell performance of 5%, which results in a power conversion efficiency of 17.1%. Optical 3D simulations based on experimentally obtained parameters were used to support the experimental findings. A good match between the simulated and experimental data was obtained, validating the model. Optical simulations reveal that the main improvement in device performance is due to a reduction in total reflection and that relative improvement in the short-circuit current density of up to 10% is possible for large-area devices. Therefore, our results present the potential of light management foils for improving the device performance of perovskite solar cells and pave the way for further use of optical simulations in the field of perovskite solar cells.
M. A. Kelly, S. Roland, Q. Zhang, Y. Lee, B. Kabius, Q. Wang, E. D. Gomez, D. Neher, W. You, “Incorporating Fluorine Substitution into Conjugated Polymers for Solar Cells: Three Different Means , Same Results”, The Journal of Physical Chemistry C 121, 2059–2068 (2017), DOI: 10.1021/acs.jpcc.6b10993
Fluorinating conjugated polymers is a proven strategy for creating high performance materials in polymer solar cells, yet few studies have investigated the importance of the fluorination method. We compare the performance of three fluorinated systems: a poly(benzodithieno-dithienyltriazole) (PBnDT-XTAZ) random copolymer where 50% of the acceptor units are difluorinated, PBnDT-mFTAZ where every acceptor unit is monofluorinated, and a 1:1 physical blend of the difluorinated and nonfluorinated polymer. All systems have the same degree of fluorination (50%) yet via different methods (chemically vs physically, random vs regular). We show that these three systems have equivalent photovoltaic behavior:,similar to 5.2% efficiency with a short-circuit current (Jsc) at ~ 11 mA/cm2, an open-circuit voltage (Voc) at 0.77 V, and a fill factor (FF) of ~ 60%. Further investigation of these three systems demonstrates that the charge generation, charge extraction, and charge transfer state are essentially identical for the three studied systems. Transmission electron microscopy shows no significant differences in the morphologies. All these data illustrate that it is possible to improve performance not only via regular or random fluorination but also by physical addition via a ternary blend. Thus, our results demonstrate the versatility of incorporating fluorine in the active layer of polymer solar cells to enhance device performance.
K. Vandewal, J. Benduhn, K. S. Schellhammer, T. Vangerven, J. E. Rückert, F. Piersimoni, R. Scholz, O. Zeika, Y. Fan, S. Barlow, D. Neher, S. R. Marder, J. Manca, D. Spoltore, G. Cuniberti, F. Ortmann, “Absorption Tails of Donor:C60 Blends Provide Insight into Thermally Activated Charge-Transfer Processes and Polaron Relaxation”, Journal of the American Chemical Society 139, 1699–1704 (2017), DOI: 10.1021/jacs.6b12857
In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)–acceptor (A) interfaces. Weak CT absorption bands for D–A complexes occur at photon energies below the optical gaps of both the donors and the C60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D–A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes.
M. Stolterfoht, C. M. Wolff, Y. Amir, A. Paulke, L. Perdigón-Toro, P. Caprioglio, D. Neher, “Approaching the fill factor Shockley–Queisser limit in stable, dopant-free triple cation perovskite solar cells”, Energy & Environmental Science 10, 1530-1539 (2017), DOI: 10.1039/C7EE00899F
Perovskite solar cells now compete with their inorganic counterparts in terms of power conversion efficiency, not least because of their small open-circuit voltage (VOC) losses. A key to surpass traditional thin-film solar cells is the fill factor (FF). Therefore, more insights into the physical mechanisms that define the bias dependence of the photocurrent are urgently required. In this work, we studied charge extraction and recombination in efficient triple cation perovskite solar cells with undoped organic electron/hole transport layers (ETL/HTL). Using integral time of flight we identify the transit time through the HTL as the key figure of merit for maximizing the fill factor (FF) and efficiency. Complementarily, intensity dependent photocurrent and VOC measurements elucidate the role of the HTL on the bias dependence of non-radiative and transport-related loss channels. We show that charge transport losses can be completely avoided under certain conditions, yielding devices with FFs of up to 84%. Optimized cells exhibit power conversion efficiencies of above 20% for 6 mm² sized pixels and 18.9% for a device area of 1 cm². These are record efficiencies for hybrid perovskite devices with dopant-free transport layers, highlighting the potential of this device technology to avoid charge-transport limitations and to approach the Shockley-Queisser limit.
M. Schubert, J. Frisch, S. Allard, E. Preis, U. Scherf, N. Koch, D. Neher, “Tuning Side Chain and Main Chain Order in a Prototypical Donor-Acceptor Copolymer: Implications for Optical, Electronic, and Photovoltaic Characteristics” in Elem. Process. Org. Photovoltaics (Ed.: K. Leo), Springer-Verlag, Berlin (2017), pp. 243–26, DOI: 10.1007/978-3-319-28338-8_10
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.
F. Laquai, D. Andrienko, C. Deibel, D. Neher, “Charge Carrier Generation, Recombination, and Extraction in Polymer-Fullerene Bulk Heterojunction Organic Solar Cells” in Elem. Process. Org. Photovoltaics (Ed.: Leo, K), Springer-Verlag, Berlin (2017), pp. 267–29, DOI: 10.1007/978-3-319-28338-8_11
In this chapter we review the basic principles of photocurrent generation in bulk heterojunction organic solar cells, discuss the loss channels limiting their efficiency, and present case studies of several polymer-fullerene blends. Using steady-state and transient, optical, and electrooptical techniques, we create a precise picture of the fundamental processes that ultimately govern solar cell efficiency.
A. Savateev, S. Pronkin, J. D. Epping, M. G. Willinger, C. Wolff, D. Neher, M. Antonietti, D. Dontsova, “Potassium Poly(heptazine imides) from Aminotetrazoles: Shifting Band Gaps of Carbon Nitride-like Materials for More Efficient Solar Hydrogen and Oxygen Evolution”, ChemCatChem 9, 167–174 (2017), DOI: 10.1002/cctc.201601165
Potassium poly(heptazine imide) (PHI) is a photocatalytically active carbon nitride material that was recently prepared from substituted 1,2,4-triazoles. Here, we show that the more acidic precursors, such as commercially available 5-aminotetrazole, upon pyrolysis in LiCl/KCl salt melt yield PHI with the greatly improved structural order and thermodynamic stability. Tetrazole-derived PHIs feature long-range crystallinities and unconventionally small layer stacking distances, leading to the altered electronic band structures as shown by Mott–Schottky analyses. Under the optimized synthesis conditions, visible-light driven hydrogen evolution rates reach twice the rate provided by the previous gold standard, mesoporous graphitic carbon nitride, which has a much higher surface area. More interestingly, the up to 0.7 V higher valence band potential of crystalline PHI compared with ordinary carbon nitrides makes it an efficient water oxidation photocatalyst, which works even in the absence of any metal-based co-catalysts under visible light. To our knowledge, this is the first case of metal-free oxygen liberation from water.
M. Stolterfoht, A. Armin, B. Philippa, D. Neher, “The Role of Space Charge Effects on the Competition between Recombination and Extraction in Solar Cells with Low-Mobility Photoactive Layers”, The Journal of Physical Chemistry Letters 7, 4716–4721 (2016), 10.1021/acs.jpclett.6b02106
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.
R. Di Pietro, I. Nasrallah, J. Carpenter, E. Gann, L.S. Kölln, L. Thomsen, D. Venkateshvaran, K. O'Hara, A. Sadhanala, M. Chabinyc, C.R. McNeill, A. Facchetti, H. Ade, H. Sirringhaus & D. Neher, “Coulomb Enhanced Charge Transport in Semicrystalline Polymer Semiconductors”, Advanced Functional Materials 26, 8011-8022 (2016), 10.1002/adfm.201602080
Polymer semiconductors provide unique possibilities and flexibility in tailoring their optoelectronic properties to match specific application demands. The recent development of semicrystalline polymers with strongly improved charge transport properties forces a review of the current understanding of the charge transport mechanisms and how they relate to the polymer's chemical and structural properties. Here, the charge density dependence of field effect mobility in semicrystalline polymer semiconductors is studied. A simultaneous increase in mobility and its charge density dependence, directly correlated to the increase in average crystallite size of the polymer film, is observed. Further evidence from charge accumulation spectroscopy shows that charges accumulate in the crystalline regions of the polymer film and that the increase in crystallite size affects the average electronic orbitals delocalization. These results clearly point to an effect that is not caused by energetic disorder. It is instead shown that the inclusion of short range coulomb repulsion between charge carriers on nanoscale crystalline domains allows describing the observed mobility dependence in agreement with the structural and optical characterization. The conclusions that are extracted extend beyond pure transistor characterization and can provide new insights into charge carrier transport for regimes and timescales that are relevant to other optoelectronic devices.
L. Fang, F. Holzmueller, T. Matulaitis, A. Baasner, C. Hauenstein, J. Benduhn, M. Schwarze, A. Petrich, F. Piersimoni, R. Scholz, O. Zeika, C. Koerner, D. Neher, K. Vandewal & K. Leo, “Fluorine-containing low-energy-gap organic dyes with low voltage losses for organic solar cells”, Synthetic Metals 222, Part B, 232-239 (2016), 10.1016/j.synthmet.2016.10.025
Fluorine-containing donor molecules TFTF, CNTF and PRTF are designed and isomer selectively synthesized for application in vacuum-deposited organic solar cells. These molecules comprise a donor-acceptor molecular architecture incorporating thiophene and benzothiadiazole derivatives as the electron-donating and electron-withdrawing moieties, respectively. As opposed to previously reported materials from this class, PRTF can be purified by vacuum sublimation at moderate to high yields because of its higher volatility and better stabilization due to a stronger intramolecular hydrogen bond, as compared to TFTF and CNTF. The UV-vis absorption spectra of the three donors show an intense broadband absorption between 500 nm and 800 nm with similar positions of their frontier energy levels. The photophysical properties of the three donor molecules are thoroughly tested and optimized in bulk heterojunction solar cells with C60 as acceptor. PRTF shows the best performance, yielding power conversion efficiencies of up to 3.8%. Moreover, the voltage loss for the PRTF device due to the non-radiative recombination of free charge carriers is exceptionally low (0.26 V) as compared to typical values for organic solar cells (> 0.34 V).
We performed an in-depth study of high molecular weight poly[3,6-(dithiophene-2-yl)-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-thieno[3,2-b]thiophene] P(DPP2OD-TT) synthesized through the Stille coupling polycondensation in order to understand the correlation between molecular weight, processing conditions and charge transport. We observed a rapid increase in its aggregation in solution with increasing molecular weight which strongly limits the solubility and processability for weight average molecular weights beyond 200 kg mol-1. This results in severe limitation in the charge transport properties of the polymer. We further observe the presence of bulk electronic defects in all different polymer batches that severely limit the current flow and manifest themselves in organic field effect transistors as apparent charge density dependence of the mobility. These defects are passivated by exposure to an ambient atmosphere, as confirmed by an increase in current and mobility that is no more charge density dependent. This is further confirmed by the result of chemical doping using 2,2-(perfluoronaphthalene-2,6-diylidene)dimalononitrile, F6TCNNQ, which leads to the filling of the trap states and a higher charge density independent mobility of up to 1 cm2V-1s-1.
G. Lu, R.D. Pietro, L.S. Kölln, I. Nasrallah, L. Zhou, S. Mollinger, S. Himmelberger, N. Koch, A. Salleo & D. Neher, “Dual-Characteristic Transistors Based on Semiconducting Polymer Blends”, Advanced Electronic Materials 2, 1600267 (2016), 10.1002/aelm.201600267
A dual-characteristic polymer field-effect transistor has markedly different characteristics in low and high voltage operations. In the low-voltage range (<5 V) it shows sharp subthreshold slopes (0.3–0.4 V/dec), using which a low-voltage inverter with gain 8 is realized, while high-voltage (>5 V) induces symmetric current with regard to drain and gate voltages, leading to discrete differential (trans) conductances.
T. Hahn, S. Tscheuschner, C. Saller, P. Strohriegl, P. Boregowda, T. Mukhopadhyay, S. Patil, D. Neher, H. Bässler & A. Köhler, “Role of Intrinsic Photogeneration in Single Layer and Bilayer Solar Cells with C60 and PCBM”, The Journal of Physical Chemistry C 120, 25083-25091 (2016), 10.1021/acs.jpcc.6b08471
In an endeavor to examine how optical excitation of C60 and PCBM contribute to the photogeneration of charge carriers in organic solar cells, we investigated stationary photogeneration in single-layer C60 and PCBM films over a broad spectrum as a function of the electric field. We find that intrinsic photogeneration starts at a photon energy of about 2.25 eV, i.e., about 0.4 eV above the first singlet excited state. It originates from charge transfer type states that can autoionize before relaxing to the lower-energy singlet S1 state, in the spirit of Onsager’s 1938 theory. We analyze the internal quantum efficiency as a function of electric field and photon energy to determine (1) the Coulombic binding and separation of the electron–hole pairs, (2) the value of the electrical gap, and (3) which fraction of photoexcitations can fully separate at a given photon energy. The latter depends on the coupling between the photogenerated charge transfer states and the eventual charge transporting states. It is by a factor of 3 lower in PCBM. Close to the threshold energy for intrinsic photoconduction (2.25 eV), the generating entity is a photogenerated electron–hole pair with roughly 2 nm separation. At higher photon energy, more expanded pairs are produced incoherently via thermalization.
P. Pingel, M. Arvind, L. Kölln, R. Steyrleuthner, F. Kraffert, J. Behrends, S. Janietz & D. Neher, “p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane”, Advanced Electronic Materials 2, 1600204 (2016), 10.1002/aelm.201600204
State-of-the-art p-type doping of organic semiconductors is usually achieved by employing strong π-electron acceptors, a prominent example being tetrafluorotetracyanoquinodimethane (F4TCNQ). Here, doping of the semiconducting model polymer poly(3-hexylthiophene), P3HT, using the strong Lewis acid tris(pentafluorophenyl)borane (BCF) as a dopant, is investigated by admittance, conductivity, and electron paramagnetic resonance measurements. The electrical characteristics of BCF- and F4TCNQ-doped P3HT layers are shown to be very similar in terms of the mobile hole density and the doping efficiency. Roughly 18% of the employed dopants create mobile holes in either F4TCNQ- or BCF-doped P3HT, while the majority of doping-induced holes remain strongly Coulomb-bound to the dopant anions. Despite similar hole densities, conductivity and hole mobility are higher in BCF-doped P3HT layers than in F4TCNQ-doped samples. This and the good solubility in many organic solvents render BCF very useful for p-type doping of organic semiconductors.
M. Zerson, M. Neumann, R. Steyrleuthner, D. Neher & R. Magerle, “Surface Structure of Semicrystalline Naphthalene Diimide–Bithiophene Copolymer Films Studied with Atomic Force Microscopy”, Macromolecules 49, 6549-6557 (2016), DOI: 10.1021/acs.macromol.6b00988
The crystallization behavior, the surface structure, and the nanomechanical properties of a semiconducting polymer play a crucial role in understanding the charge injection process, the transport of the charge carriers and the processability of the material. Here we study the semiconducting copolymer poly([N,N′-bis(2-octyldodecyl)-11-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5′-(2,2′-12 bithiophene)) (P(NDI2OD-T2)) and investigate the influence of annealing conditions on its surface structure through intermittent contact mode atomic force microscopy (AFM) and AFM-based measurements of amplitude–phase–distance (APD) curves. For spin-cast thin films as well as for films annealed at temperatures up to 320 °C, we find that the edges of crystalline lamellae are exposed at the surface. A 1.2 nm thick layer of alkyl side chains covers the film surface as indicated by the tip indentation. This suggests that charge injection into P(NDI2OD-T2) films is not hindered by a surface layer of amorphous material. In 5 nm thick films, corresponding to two monolayers of P(NDI2OD-T2), after annealing at 320 °C, crystalline lamella also orient perpendicular to the film plane with the (100) surfaces oriented parallel to the film plane. The lamellae form ∼100 nm large areas (terraces) with uniform lamella height. The step height between adjacent terraces is 2.2 nm, and we attribute it to monomolecular steps between the molecular thin layers of edge-on-oriented polymer chains. This well-defined molecular conformation at the film surface with the chain backbone and the π-stacking direction oriented in the film plane is presumably an important factor contributing to the exceptional performance of P(NDI2OD-T2) in bottom-gate organic field-effect transistors.
L. Müller, D. Nanova, T. Glaser, S. Beck, A. Pucci, A.K. Kast, R.R. Schröder, E. Mankel, P. Pingel, D. Neher, W. Kowalsky & R. Lovrincic, “Charge-Transfer–Solvent Interaction Predefines Doping Efficiency in p-Doped P3HT Films”, Chemistry of Materials 28, 4432-4439 (2016), DOI: 10.1021/acs.chemmater.6b01629
Efficient electrical doping of organic semiconductors is a necessary prerequisite for the fabrication of high performance organic electronic devices. In this work, we study p-type doping of poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) spin-cast from two different solvents. Using electron diffraction, we find strong dopant-induced π–π-stacking for films from the solvent chloroform, but not from chlorobenzene. This image is confirmed and expanded by the analysis of vibrational features of P3HT and polaron absorptions using optical spectroscopy. Here, a red-shifted polaron absorption is found in doped films from chloroform, caused by a higher conjugation length of the polymer backbone. These differences result in a higher conductivity of films from chloroform. We use optical spectroscopy on the corresponding blend solutions to shed light on the origin of this effect and propose a model to explain why solutions of doped P3HT reveal more aggregation of charged molecules in chlorobenzene, whereas more order is finally observed in dried films from chloroform. Our study emphasizes the importance of solvent parameters exceeding the bare solubility of pure dopant and host material for the preparation of highly conductive doped films.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
D. Neher, J. Kniepert, A. Elimelech & L.J.A. Koster, “A New Figure of Merit for Organic Solar Cells with Transport-limited Photocurrents”, Scientific Reports 6, 24861 (2016), DOI: 10.1038/srep24861 • PDF • Supporting Info
Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit α to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor.
A. Paulke, S.D. Stranks, J. Kniepert, J. Kurpiers, C.M. Wolff, N. Schön, H.J. Snaith, T.J.K. Brenner & D. Neher, “Charge carrier recombination dynamics in perovskite and polymer solar cells”, Applied Physics Letters 108, 113505 (2016), DOI: 10.1063/1.4944044 • PDF
Time-delayed collection field experiments are applied to planar organometal halide perovskite (CH3NH3PbI3) based solar cells to investigate charge carrier recombination in a fully working solar cell at the nanosecond to microsecond time scale. Recombination of mobile (extractable) charges is shown to follow second-order recombination dynamics for all fluences and time scales tested. Most importantly, the bimolecular recombination coefficient is found to be time-dependent, with an initial value of ca. 10−9 cm3/s and a progressive reduction within the first tens of nanoseconds. Comparison to the prototypical organic bulk heterojunction device PTB7:PC71BM yields important differences with regard to the mechanism and time scale of free carrier recombination.
J. Kurpiers, D.M. Balazs, A. Paulke, S. Albrecht, I. Lange, L. Protesescu, M.V. Kovalenko, M.A. Loi & D. Neher, “Free carrier generation and recombination in PbS quantum dot solar cells”, Applied Physics Letters 108, 103102 (2016), DOI: 10.1063/1.4943379 • PDF
Time Delayed Collection Field and Bias Assisted Charge Extraction (BACE) experiments are used to investigate the charge carrier dynamics in PbS colloidal quantum dot solar cells. We find that the free charge carrier creation is slightly field dependent, thus providing an upper limit to the fill factor. The BACE measurements reveal a rather high effective mobility of 2×10-3 cm2/Vs, meaning that charge extraction is efficient. On the other hand, a rather high steady state non-geminate recombination coefficient of 3×10-10 cm3/s is measured. We, therefore, propose a rapid free charge recombination to constitute the main origin for the limited efficiency of the PbS colloidal quantum dots cells.
G. Ligorio, M.V. Nardi, R. Steyrleuthner, D. Ihiawakrim, N. Crespo-Monteiro, M. Brinkmann, D. Neher & N. Koch, “Metal nanoparticle mediated space charge and its optical control in an organic hole-only device”, Applied Physics Letters 108, 153302 (2016), DOI: 10.1063/1.4945710 • PDF
We reveal the role of localized space charges in hole-only devices based on an organic semiconductor with embedded metal nanoparticles (MNPs). MNPs act as deep traps for holes and reduce the current density compared to a device without MNPs by a factor of 104 due to the build-up of localized space charge. Dynamic MNPs charged neutrality can be realized during operation by electron transfer from excitons created in the organic matrix, enabling light sensing independent of device bias. In contrast to the previous speculations, electrical bistability in such devices was not observed.
A.M. Anton, R. Steyrleuthner, W. Kossack, D. Neher & F. Kremer, “Spatial Orientation and Order of Structure-Defining Subunits in Thin Films of a High Mobility n-Type Copolymer”, Macromolecules 49, 1798-1806 (2016), DOI: 10.1021/acs.macromol.5b02420
Orientation and order of distinct molecular subunits in solid layers of the high mobility n-type copolymer poly[N,N′-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-5,5′-(2,2′-bithiophene) P(NDI2OD-T2) are investigated by means of infrared transition moment orientational analysis. This novel spectroscopic technique based on concurrent absorbance measurements of structure-specific bands in dependence on inclination and polarization of the incoming light enables to determine the complete tensor of absorption independently for each transition moment. As a result, for nanometer thin films pronounced in-plane anisotropy arising from self-aggregated order is detected, which, however, is no longer discernible for micrometer thick samples. In contrast, the out-of-plane orientation (inclination of molecular subunits) is retained irrespective of the widely varying layer thicknesses (150 nm vs 1.4 μm). Thus, the conception of the sample morphology occurs as stratification of slightly misaligned layers of oriented polymers; with increasing film thickness the macroscopic in-plane order diminishes, whereas the out-of-plane orientation is preserved.
G. Lu, N. Koch & D. Neher, “In-situ tuning threshold voltage of field-effect transistors based on blends of poly(3-hexylthiophene) with an insulator electret”, Applied Physics Letters 107, 063301 (2015), DOI: 10.1063/1.4928554 • PDF
Blending the conjugated polymer poly(3-hexylthiophene) (P3HT) with the insulating electret polystyrene (PS), we show that the threshold voltage Vt of organic field-effect transistors (OFETs) can be easily and reversely tuned by applying a gate bias stress at 130°C. It is proposed that this phenomenon is caused by thermally activated charge injection from P3HT into PS matrix, and that this charge is immobilized within the PS matrix after cooling down to room temperature. Therefore, room-temperature hysteresis-free FETs with desired Vt can be easily achieved. The approach is applied to reversely tune the OFET mode of operation from accumulation to depletion, and to build inverters.
J. Xu, M. Shalom, F. Piersimoni, M. Antonietti, D. Neher & T.J.K. Brenner, “Color-Tunable Photoluminescence and NIR Electroluminescence in Carbon Nitride Thin Films and Light-Emitting Diodes”, Advanced Optical Materials 3, 913-917 (2015), DOI: 10.1002/adom.201500019
Color-tunable photoluminescence from continuous graphitic carbon nitride (g-C3N4) thin films is demonstrated. The films are employed in light-emitting diodes. A strong redshift of the electroluminescence with respect to photoluminescence is observed and a model for this uncommon behavior is provided.
D. Bartesaghi, I.d.C. Perez, J. Kniepert, S. Roland, M. Turbiez, D. Neher & L.J.A. Koster, “Competition between recombination and extraction of free charges determines the fill factor of organic solar cells”, Nature Communications 6, 7083 (2015), DOI: 10.1038/ncomms8083 • PDF • Supporting Info
Among the parameters that characterize a solar cell and define its power-conversion efficiency, the fill factor is the least well understood, making targeted improvements difficult. Here we quantify the competition between charge extraction and recombination by using a single parameter [theta], and we demonstrate that this parameter is directly related to the fill factor of many different bulk-heterojunction solar cells. Our finding is supported by experimental measurements on 15 different donor:acceptor combinations, as well as by drift-diffusion simulations of organic solar cells in which charge-carrier mobilities, recombination rate, light intensity, energy levels and active-layer thickness are all varied over wide ranges to reproduce typical experimental conditions. The results unify the fill factors of several very different donor:acceptor combinations and give insight into why fill factors change so much with thickness, light intensity and materials properties. To achieve fill factors larger than 0.8 requires further improvements in charge transport while reducing recombination.
A.M. Anton, R. Steyrleuthner, W. Kossack, D. Neher & F. Kremer, “Infrared Transition Moment Orientational Analysis on the Structural Organization of the Distinct Molecular Subunits in Thin Layers of a High Mobility n-Type Copolymer”, Journal of the American Chemical Society 137, 6034-6043 (2015), DOI: 10.1021/jacs.5b01755 • PDF • Supporting Info
The IR-based method of infrared transition moment orientational analysis (IR-TMOA) is employed to unravel molecular order in thin layers of the semiconducting polymer poly[N,N'-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) (P(NDI2OD-T2)). Structure-specific vibrational bands are analyzed in dependence on polarization and inclination of the sample with respect to the optical axis. By that the molecular order parameter tensor for the respective molecular moieties with regard to the sample coordinate system is deduced. Making use of the specificity of the IR spectral range, we are able to determine separately the orientation of atomistic planes defined through the naphthalenediimide (NDI) and bithiophene (T2) units relative to the substrate, and hence, relative to each other. A pronounced solvent effect is observed: While chlorobenzene causes the T2 planes to align preferentially parallel to the substrate at an angle of 29°, using a 1:1 chloronaphthalene:xylene mixture results in a reorientation of the T2 units from a face on into an edge on arrangement. In contrast the NDI unit remains unaffected. Additionally, for both solvents evidence is observed for the aggregation of chains in accord with recently published results obtained by UV-vis absorption spectroscopy.
U. Würfel, D. Neher, A. Spies & S. Albrecht, “Impact of charge transport on current-voltage characteristics and power-conversion efficiency of organic solar cells”, Nature Communications 6, 6951 (2015), DOI: 10.1038/ncomms7951 • PDF • Supporting Info
This work elucidates the impact of charge transport on the photovoltaic properties of organic solar cells. Here we show that the analysis of current-voltage curves of organic solar cells under illumination with the Shockley equation results in values for ideality factor, photocurrent and parallel resistance, which lack physical meaning. Drift-diffusion simulations for a wide range of charge-carrier mobilities and illumination intensities reveal significant carrier accumulation caused by poor transport properties, which is not included in the Shockley equation. As a consequence, the separation of the quasi Fermi levels in the organic photoactive layer (internal voltage) differs substantially from the external voltage for almost all conditions. We present a new analytical model, which considers carrier transport explicitly. The model shows excellent agreement with full drift-diffusion simulations over a wide range of mobilities and illumination intensities, making it suitable for realistic efficiency predictions for organic solar cells.
J. Kniepert, I. Lange, J. Heidbrink, J. Kurpiers, T.J.K. Brenner, L.J.A. Koster & D. Neher, “Effect of Solvent Additive on Generation, Recombination, and Extraction in PTB7:PCBM Solar Cells: A Conclusive Experimental and Numerical Simulation Study”, The Journal of Physical Chemistry C 119, 8310-8320 (2015), DOI: 10.1021/jp512721e • PDF • Supporting Info
Time-delayed collection field (TDCF), bias-assisted charge extraction (BACE), and space charge-limited current (SCLC) measurements are combined with complete numerical device simulations to unveil the effect of the solvent additive 1,8-diiodooctane (DIO) on the performance of PTB7:PCBM bulk heterojunction solar cells. DIO is shown to increase the charge generation rate, reduce geminate and bimolecular recombination, and increase the electron mobility. In total, the reduction of loss currents by processing with the additive raises the power conversion efficiency of the PTB7:PCBM blend by a factor of almost three. The lower generation rates and higher geminate recombination losses in devices without DIO are consistent with a blend morphology comprising large fullerene clusters embedded within a PTB7-rich matrix, while the low electron mobility suggests that these fullerene clusters are themselves composed of smaller pure fullerene aggregates separated by disordered areas. Our device simulations show unambiguously that the effect of the additive on the shape of the current–voltage curve (J–V) cannot be ascribed to the variation of only the mobility, the recombination, or the field dependence of generation. It is only when the changes of all three parameters are taken into account that the simulation matches the experimental J–V characteristics under all illumination conditions and for a wide range of voltages.
L. Lysyakova, N. Lomadze, D. Neher, K. Maximova, A.V. Kabashin & S. Santer, “Light-Tunable Plasmonic Nanoarchitectures Using Gold Nanoparticle–Azobenzene-Containing Cationic Surfactant Complexes”, The Journal of Physical Chemistry C 119, 3762-3770 (2015), DOI: 10.1021/jp511232g
When arranged in a proper nanoaggregate architecture, gold nanoparticles can offer controllable plasmon-related absorption/scattering, yielding distinct color effects that depend critically on the relative orientation and distance between nanoparticle constituents. Herein, we report on the implementation of novel plasmonic nanoarchitectures based on complexes between gold nanoparticles and an azobenzene-modified cationic surfactant that can exhibit a light-tunable plasmonic response. The formation of such complexes becomes possible through the use of strongly negatively charged bare gold nanoparticles (~10 nm diameter) prepared by the method of laser ablation in deionized water. Driven by electrostatic interactions, the cationic surfactant molecules attach and form a shell around the negatively charged nanoparticles, resulting in neutralization of the particle charge or even overcompensation beyond which the nanoparticles become positively charged. At low and high surfactant concentrations, Au nanoparticles are negatively and positively charged, respectively, and are represented by single species due to electric repulsion effects having absorption peaks around 523–527 nm, whereas at intermediate concentrations, the Au nanoparticles become neutral, forming nanoscale 100-nm clusterlike aggregates and exhibiting an additional absorption peak at λ > 600 nm and a visible change in the color of the solution from red to blue. Because of the presence of the photosensitive azobenzene unit in the surfactant tail that undergoes trans-to-cis isomerization under irradiation with UV light, we then demonstrate a light-controlled nanoclustering of nanoparticles, yielding a switch in the plasmonic absorption band and a related change in the solution color. The formed hybrid architectures with a light-controlled plasmonic response could be important for a variety of tasks, including biomedical, surface-enhanced Raman spectroscopy (SERS), data transmission, and storage applications.
F. Piersimoni, R. Schlesinger, J. Benduhn, D. Spoltore, S. Reiter, I. Lange, N. Koch, K. Vandewal & D. Neher, “Charge Transfer Absorption and Emission at ZnO/Organic Interfaces”, The Journal of Physical Chemistry Letters 6, 500-504 (2015), DOI: 10.1021/jz502657z
We investigate hybrid charge transfer states (HCTS) at the planar interface between α-NPD and ZnO by spectrally resolved electroluminescence (EL) and external quantum efficiency (EQE) measurements. Radiative decay of HCTSs is proven by distinct emission peaks in the EL spectra of such bilayer devices in the NIR at energies well below the bulk α-NPD or ZnO emission. The EQE spectra display low energy contributions clearly red-shifted with respect to the α-NPD photocurrent and partially overlapping with the EL emission. Tuning of the energy gap between the ZnO conduction band and α-NPD HOMO level (Eint) was achieved by modifying the ZnO surface with self-assembled monolayers based on phosphonic acids. We find a linear dependence of the peak position of the NIR EL on Eint, which unambiguously attributes the origin of this emission to radiative recombination between an electron on the ZnO and a hole on α-NPD. In accordance with this interpretation, we find a strictly linear relation between the open-circuit voltage and the energy of the charge state for such hybrid organic/inorganic interfaces.
I. Lange, S. Reiter, J. Kniepert, F. Piersimoni, M. Pätzel, J. Hildebrandt, T. Brenner, S. Hecht & D. Neher, “Zinc oxide modified with benzylphosphonic acids as transparent electrodes in regular and inverted organic solar cell structures”, Applied Physics Letters 106, 113302 (2015), DOI: 10.1063/1.4916182 • PDF
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.
S. Roland, S. Neubert, S. Albrecht, B. Stannowski, M. Seger, A. Facchetti, R. Schlatmann, B. Rech & D. Neher, “Hybrid Organic/Inorganic Thin-Film Multijunction Solar Cells Exceeding 11% Power Conversion Efficiency”, Advanced Materials 27, 1262-1267 (2015), DOI: 10.1002/adma.201404698
Hybrid multijunction solar cells comprising hydrogenated amorphous silicon and an organic bulk heterojunction are presented, reaching 11.7% power conversion efficiency. The benefits of merging inorganic and organic subcells are pointed out, the optimization of the cells, including optical modeling predictions and tuning of the recombination contact are described, and an outlook of this technique is given.
F.S.U. Fischer, D. Trefz, J. Back, N. Kayunkid, B. Tornow, S. Albrecht, K.G. Yager, G. Singh, A. Karim, D. Neher, M. Brinkmann & S. Ludwigs, “Highly Crystalline Films of PCPDTBT with Branched Side Chains by Solvent Vapor Crystallization: Influence on Opto-Electronic Properties”, Advanced Materials 27, 1223-1228 (2015), DOI: 10.1002/adma.201403475
PCPDTBT, a marginally crystallizable polymer, is crystallized into a new crystal structure using solvent-vapor annealing. Highly ordered areas with three different polymer-chain orientations are identified using TEM/ED, GIWAXS, and polarized Raman spectroscopy. The optical and structural properties differ significantly from films prepared by standard device preparation protocols. Bilayer solar cells, however, show similar performance.
F. Ghani, A. Opitz, P. Pingel, G. Heimel, I. Salzmann, J. Frisch, D. Neher, A. Tsami, U. Scherf & N. Koch, “Charge transfer in and conductivity of molecularly doped thiophene-based copolymers”, Journal of Polymer Science Part B: Polymer Physics 53, 58-63 (2015), DOI: 10.1002/polb.23631
The electrical conductivity of organic semiconductors can be enhanced by orders of magnitude via doping with strong molecular electron acceptors or donors. Ground-state integer charge transfer and charge-transfer complex formation between organic semiconductors and molecular dopants have been suggested as the microscopic mechanisms causing these profound changes in electrical materials properties. Here, we study charge-transfer interactions between the common molecular p-dopant 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane and a systematic series of thiophene-based copolymers by a combination of spectroscopic techniques and electrical measurements. Subtle variations in chemical structure are seen to significantly impact the nature of the charge-transfer species and the efficiency of the doping process, underlining the need for a more detailed understanding of the microscopic doping mechanism in organic semiconductors to reliably guide targeted chemical design.