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W e would like to start off by thanking the authors of the comment, Wetzelaer and Blom, for their very helpful and constructive analysis. They present an interesting alternative view on an important and timely research topic. Before discussing the mechanism suggested in their comment, from the viewpoint of our experimental results, we would like to summarize our findings. In our work, 1 we experimentally showed that • The contact between donor molecules in the active layer of organic solar cells (OSCs) and a molybdenum oxide (MoO 3) hole extraction layer (HEL) causes an increase in nonradiative recombination losses, proportional to the extent of contacts. • We attributed these losses to surface recombination, and we proved that the losses can be suppressed by inserting a thin interfacial fullerene layer at the anode side. • Analyzing various donor−acceptor mixing ratios, with and without a fullerene-modified HEL, we decoupled and quantified the contribution from surface recombi-nation on the total nonradiative losses occurring in these devices. In the best case, we showed an improvement of 150 meV in V OC , as compared to the reference device. This demonstrates that surface recombination is a considerable contributor to nonradiative voltage losses in these solar cells, which are otherwise commonly occurring through charge-transfer states or energetic trap states because of defects in the bulk. We consider this the main result of our work. • Measurements by a modified charge extraction by linearly increasing voltage (CELIV) technique provided evidence that the improvement in V OC could be attributed to an enhanced built-in potential (V bi), reducing the presence of minority charge carriers at the respective electrodes. Although the authors of the comment in general agree with our experimental findings, they argue that the V bi does not play a direct role in suppressing the surface recombination of minority carriers. The introduction of a C 60 interlayer, they argue, renders the MoO 3 contact ohmic. 2 The reduced anodic injection barrier simultaneously increases the V bi , minimizes nonradiative voltage losses upon the extraction of majority carriers (holes), and suppresses minority-carrier (electron) surface recombination, the latter being the result of hole accumulation and associated band bending near the ohmic hole contact. Therefore, the ohmic contact formation suppresses both majority-and minority-carrier surface recombination losses, whereas the built-in voltage per se, they reason, does not play a major role. It is our opinion that the authors of the comment provide a very reasonable alternative explanation for the reduced surface recombination. Injection barriers at the contacts are well-known to be detrimental for the performance of OSC as being a major cause of a reduced V bi and increased surface recombination. Injection barriers have been shown to reduce not only the V OC but also the fill factor (FF), sometimes even leading to s-shaped JV curves. 3−5 It has been suggested that, in the case of very large injection barriers, the V OC is given by V bi. 6,7 Although V bi is determined by the difference in the work functions of the contacts, because of Fermi level pinning and the associated band bending, the built-in potential across the active layer, the effective V bi , typically cannot exceed the effective gap of the bulk-heterojunction blend. In other words, the anode Fermi level pins to the highest occupied molecular orbital (HOMO) of the donor, whereas the cathode pins to the lowest unoccupied molecular orbital (LUMO) of the acceptor. In addition, because of disorder, Fermi level pinning typically occurs to discrete gap or tail states, causing additional band bending, which further limits the effective V bi. 8,9 If there is an injection barrier at one contact, an increase or decrease in this barrier is directly reflected in the V bi. 5 Sachsische Aufbaubank [100325708]; Academy of FinlandAcademy of Finland

Omnipresent quality monitoring in food products, blood-oxygen measurement in lightweight conformal wrist bands, or data-driven automated industrial production: Innovation in many fields is being empowered by sensor technology. Specifically, organic photodetectors (OPDs) promise great advances due to their beneficial properties and low-cost production. Recent research has led to rapid improvement in all performance parameters of OPDs, which are now on-par or better than their inorganic counterparts, such as silicon or indium gallium arsenide photodetectors, in several aspects. In particular, it is possible to directly design OPDs for specific wavelengths. This makes expensive and bulky optical filters obsolete and allows for miniature detector devices. In this review, recent progress of such narrowband OPDs is systematically summarized covering all aspects from narrow-photo-absorbing materials to device architecture engineering. The recent challenges for narrowband OPDs, like achieving high responsivity, low dark current, high response speed, and good dynamic range are carefully addressed. Finally, application demonstrations covering broadband and narrowband OPDs are discussed. Importantly, several exciting research perspectives, which will stimulate further research on organic-semiconductor-based photodetectors, are pointed out at the very end of this review.

Wavelength-discriminating systems typically consist of heavy benchtop-based instruments, comprising diffractive optics, moving parts, and adjacent detectors. For simple wavelength measurements, such as lab-on-chip light source calibration or laser wavelength tracking, which do not require polychromatic analysis and cannot handle bulky spectroscopy instruments, lightweight, easy-to-process, and flexible single-pixel devices are attracting increasing attention. Here, a device is proposed for monotonously transforming wavelength information into the time domain with room-temperature phosphorescence at the heart of its functionality, which demonstrates a resolution down to 1 nm and below. It is solution-processed from a single host-guest system comprising organic room-temperature phosphors and colloidal quantum dots. The share of excited triplet states within the photoluminescent layer is dependent on the excitation wavelength and determines the afterglow intensity of the film, which is tracked by a simple photodetector. Finally, an all-organic thin-film wavelength sensor and two applications are demonstrated where this novel measurement concept successfully replaces a full spectrometer.

Charge selective interlayers are crucial in thin-film photovoltaics, such as organic and Perovskite solar cells. Charge transporting layers (doped and undoped) constitute perhaps the most important class of charge selective interlayers; however, it is not well understood how a charge transporting layer should be designed in order to ensure efficient extraction of majority carriers while blocking minority carriers. This work clarifies how well charge-transporting layers with varying majority carrier conductivities block minority carriers. We use the Charge Extraction by a Linearly Increasing Voltage technique to determine the surface recombination velocity of minority carriers in model system devices with varying majority carrier conductivity in the transporting layer. Our results show that transporting layers with high conductivity for majority carriers do not block minority carriers - at least not at operating voltages close to or above the built-in voltage, due to direct bi-molecular recombination across the transporting layer-absorber layer interface. We furthermore discuss and propose design principles to achieve selective charge extraction in thin film solar cells using charge transporting layers.

Charge injection from electrodes into doped organic films is a widespread technology used in the majority of state-of-the-art organic semiconductor devices. Although such interfaces are commonly considered to form Ohmic contacts via strong band bending, an experiment that directly measures the contact resistance has not yet been demonstrated. In this study, we use a simple metal/doped organic semiconductor/metal stack and study its voltage-dependent resistance. A transport layer thickness variation proves that the presented experiment gains direct access to the contact resistance of the device. We can quantify that for an operating current density of 10mA/cm2 the investigated material system exhibits a voltage drop over the metal/organic interface of about 200mV, which can be reduced by more than one order of magnitude when employing an additional injection layer. The presented experiment proposes a simple strategy to measure the contact resistance between any metal and doped organic film without applying numerical tools or elaborate techniques. Furthermore, the simplistic device architecture allows for very high, homogeneous, and tunable electric fields within the organic layer, which enables a clear investigation of the Poole-Frenkel effect.

Charge generation and recombination processes at interfaces between electron donating (donor, D) and accepting molecules (acceptor, A) are mediated by intermolecular charge-transfer (CT) states. Si...

A significant number of organic electronic devices rely on blends of electron-donating and electron-accepting molecules. In bulk heterojunction organic photovoltaics, the nanoscopic phase behavior of the two individual components within the photoactive layer has a major impact on the charge separation and charge transport properties. For polymer:fullerene solar cells, it has been hypothesized that an increased accessibility of the electron-deficient monomer unit in push-pull type low bandgap polymers allows for fullerene ‘docking’. The close proximity of electron donor and acceptor molecules enables more efficient charge transfer, which is beneficial for the device efficiency. With this in mind, we synthesized a series of PBDTTPD [poly(benzodithiophene-thienopyrroledione)] low bandgap copolymers with varying side chains. Solar cells were fabricated for all polymers and the device characteristics were compared. The combination of proton wideline solid-state NMR (ssNMR) relaxometry and sensitive external quantum efficiency (sEQE) measurements was shown to provide essential information on donor-acceptor interactions and phase separation in bulk heterojunction organic photovoltaics. The reduced charge transfer state absorption and the observed phase separation of crystalline PC71BM domains for the polymers containing the most accessible methyl-TPD unit indicate a diminished contact between donor and acceptor, leading to a loss in performance.

The energetic landscape of charge transfer (CT) states at the interface of electron donating and electron accepting domains in organic optoelectronic devices is crucial for their performance. Central questions -- such as the role of static energetic disorder and vibrational effects -- are under ongoing dispute. This study provides an in-depth analysis of temperature dependent broadening of the spectroscopic absorption and emission features of CT states in devices with small molecule-fullerene blends. We confirm the validity of the electro-optical reciprocity relation between the photovoltaic external quantum efficiency ($\mathrm{EQE_{PV}}$) and electroluminescence ($\mathrm{EQE_{EL}}$), enabling us to validate the device temperature during the experiment. The validated temperature allows us to fit our experimental data with several models, and compare extracted CT state energies with the corresponding open circuit voltage limit at $0\mathrm{\,K}$. Our findings unveil that the absorption and emission characteristics are usually not symmetric, and dominated by temperature-activated broadening (vibrational) effects instead of static disorder., 11 pages, 5 figures submitted to: Physical Review Applied

Organic solar cells are approaching power conversion efficiencies of other thin‐film technologies. However, in order to become truly market competitive, the still substantial voltage losses need to be reduced. Here, the synthesis and characterization of four novel arylamine‐based push‐pull molecular donors was described, two of them exhibiting a methyl group at the para‐position of the external phenyl ring of the arylamine block. Assessing the charge‐transfer state properties and the effects of methylation on the open‐circuit voltage of the device showed that devices based on methylated versions of the molecular donors exhibited reduced voltage losses due to decreased non‐radiative recombination. Modelling suggested that methylation resulted in a tighter interaction between donor and acceptor molecules, turning into a larger oscillator strength to the charge‐transfer states, thereby ensuing reduced non‐radiative decay rates., Structural tuning improves efficiency: Modification of the molecular structure of organic molecules allows to influence the performance of organic photovoltaic devices. Addition of a methyl group in the para‐position of the external phenyl ring leads to increase in open‐circuit voltage. Quantum‐chemical calculations attribute this effect to the increase of the oscillator strength of the electronic transition between the donor and acceptor.

Organic near-infrared (NIR) detectors have potential applications in biomedicine, agriculture, and manufacturing industries to identify and quantify materials contactless, in real time and at a low cost. Recently, tunable narrow-band NIR sensors based on charge-transfer state absorption of bulk-heterojunctions embedded into Fabry-Perot micro-cavities have been demonstrated. In this work, this type of sensor is further miniaturized by stacking two sub-cavities on top of each other. The resulting three-terminal device detects and distinguishes photons at two specific wavelengths. By varying the thickness of each sub-cavity, the detection ranges of the two sub-sensors are tuned independently between 790 and 1180, and 1020 and 1435 nm, respectively, with full-width-at-half-maxima ranging between 35 and 61 nm. Transfer matrix modeling is employed to select and optimize device architectures with a suppressed cross-talk in the coupled resonator system formed by the sub-cavities, and thus to allow for two distinct resonances. These stacked photodetectors pave the way for highly integrated, bi-signal spectroscopy tunable over a broad NIR range. To demonstrate the application potential, the stacked dual sensor is used to determine the ethanol concentration in a water solution. The authors acknowledge the DFG project VA 1035/5-1 (Photogen) and the Sachsische Aufbaubank through project no. 100325708 (InfraKart). The authors acknowledge Rico Meerheim and Paul Vince for fruitful discussions. Open access funding enabled and organized by Projekt DEAL. Wang, YZ (corresponding author), Tech Univ Dresden, Dresden Integrated Ctr Appl Phys & Photon Mat IAP, Nothnitzer Str 61, D-01187 Dresden, Germany. Tech Univ Dresden, Inst Appl Phys, Nothnitzer Str 61, D-01187 Dresden, Germany. Vandewal, K (corresponding author), Hasselt Univ, Inst Mat Res IMO IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium. yazhong.wang@tu-dresden.de; koen.vandewal@uhasselt.be

Organic solar cells usually utilise a heterojunction between electron-donating (D) and electron-accepting (A) materials to split excitons into charges. However, the use of D-A blends intrinsically limits the photovoltage and introduces morphological instability. Here, we demonstrate that polycrystalline films of chemically identical molecules offer a promising alternative and show that photoexcitation of α-sexithiophene (α-6T) films results in efficient charge generation. This leads to α-6T based homojunction organic solar cells with an external quantum efficiency reaching up to 44% and an open-circuit voltage of 1.61 V. Morphological, photoemission, and modelling studies show that boundaries between α-6T crystalline domains with different orientations generate an electrostatic landscape with an interfacial energy offset of 0.4 eV, which promotes the formation of hybridised exciton/charge-transfer states at the interface, dissociating efficiently into free charges. Our findings open new avenues for organic solar cell design where material energetics are tuned through molecular electrostatic engineering and mesoscale structural control., Though single-material organic solar cells are attractive for next-generation photovoltaic technologies, designing new materials with ideal properties remains a challenge. Here, the authors report the use of orientation-dependent molecular electrostatics to realise efficient homojunction devices.

The low-energy edge of optical absorption spectra is critical for the performance of solar cells, but is not well understood in the case of organic solar cells (OSCs). We study the microscopic origin of exciton bands in molecular blends and investigate their role in OSCs. We simulate the temperature dependence of the excitonic density of states and low-energy absorption features, including low-frequency molecular vibrations and multi-exciton hybridisation. For model donor-acceptor blends featuring charge-transfer excitons, our simulations agree very well with temperature-dependent experimental absorption spectra. We unveil that the quantum effect of zero-point vibrations, mediated by electron-phonon interaction, causes a substantial exciton bandwidth and reduces the open-circuit voltage, which is predicted from electronic and vibronic molecular parameters. This effect is surprisingly strong at room temperature and can substantially limit the OSC's efficiency. Strategies to reduce these vibration-induced voltage losses are discussed for a larger set of systems and different heterojunction geometries.

Organic photodetectors (OPDs) with a performance comparable to that of conventional inorganic ones have recently been demonstrated for the visible regime. However, near-infrared photodetection has proven to be challenging and, to date, the true potential of organic semiconductors in this spectral range (800-2500 nm) remains largely unexplored. In this work, it is shown that the main factor limiting the specific detectivity (D*) is non-radiative recombination, which is also known to be the main contributor to open-circuit voltage losses. The relation between open-circuit voltage, dark current, and noise current is demonstrated using four bulk-heterojunction devices based on narrow-gap donor polymers. Their maximum achievableD* is calculated alongside a large set of devices to demonstrate an intrinsic upper limit ofD* as a function of the optical gap. It is concluded that OPDs have the potential to be a useful technology up to 2000 nm, given that high external quantum efficiencies can be maintained at these low photon energies. Vandewal, K (corresponding author), UHasselt Hasselt Univ, Inst Mat Res IMO, Agoralaan 1,Bldg D, B-3590 Diepenbeek, Belgium ; IMEC, Associated Lab IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium. Armin, A (corresponding author), Swansea Univ, Dept Phys, Singleton Pk, Swansea SA2 8PP, W Glam, Wales. ardalan.armin@swansea.ac.uk; koen.vandewal@uhasselt.be

The origin of energetic disorder in organic semiconductors and its impact on opto-electronic properties remains a topic of intense controversy. Particularly the disorder at electron donor-acceptor interfaces for organic photovoltaics is pivotal to understand as it is expected to affect photo-carrier generation, recombination and consequently device efficiency parameters. In this work we evaluate the temperature dependence of the line-shape of the photoluminescence (PL) and electroluminescence (EL) spectra of small molecule:fullerene blend devices, with the ambition to disentangle dynamic and static disorder contributions. The EL emission spectra are dominated by charge-transfer (CT) state emission and are confirmed to be of Gaussian character and almost completely voltage independent. More importantly, a strong line-width narrowing is persistently observed upon cooling, down to a certain material specific low temperature, below which the line-width remains constant. It is consequently clear that the main portion of the line-width measured at operating conditions of room temperature or higher, is originating from thermally activated, or dynamic, disorder. The observed temperature dependence of the high-energy emission tail can be fully described by taking into account high and low frequency molecular vibrational modes, without having to rely on static disorder. The presence of low frequency molecular modes with large Huang-Rhys factors results in a Gaussian line-shape, which is additionally broadened at high temperature by thermal population of high frequency intra-molecular modes. We therefore cast strong doubts regarding the commonly used assumption that single temperature optical measurements of absorption or emission tails are able to provide meaningful information regarding the shape of a static density of states tail. K. T. acknowledges the German Research Foundation (DFG) through project 382633022 (RECOLPER) and the Experimental Physics VI chair of Prof. Vladimir Dyakonov at Wurzburg University. J. B. acknowledges the DFG project VA 1035/5-1 (Photogen) and the Sachsische Aufbaubank through project no. 100325708 (Infrakart). The authors also acknowledge discussion on the topic with Robert Street, Thomas Kirchartz, Frank Ortmann and Carsten Deibel. Tvingstedt, K (corresponding author), Julius Maximilian Univ Wurzburg, Expt Phys 6, D-97074 Wurzburg, Germany. ktvingstedt@physik.uni-wuerzburg.de

Diketopyrrolopyrrole (DPP)-based donor acceptor copolymers have gained a significant amount of research interest in the organic electronics community because of their high charge carrier mobilities in organic field-effect transistors (OFETs) and their ability to harvest near-infrared (NIR) photons in solar cells. In this study, we have synthesized four DPP based donor-acceptor copolymers with variations in the donor unit and the branching point of the solubilizing alkyl chains (at the second or sixth carbon position). Grazing incidence wide-angle X-ray scattering (GIWAXS) results suggest that moving the branching point further away from the polymer backbone increases the tendency for aggregation and yields polymer phases with a higher degree of crystallinity (DoC). The polymers were blended with PC70BM and used as active layers in solar cells. A careful analysis of the energetics of the neat polymer and blend films reveals that the charge-transfer state energy (E-CT) of the blend films lies exceptionally close to the singlet energy of the donor (E-D*), indicating near zero electron transfer losses. The difference between the optical gap and open-circuit voltage (V-OC) is therefore determined to be due to rather high nonradiative 418 +/- 13 mV) and unavoidable radiative voltage losses (approximate to 255 +/- 8 mV). Even though the four materials have similar optical gaps, the short-circuit current density (J(SC)) covers a vast span from 7 to 18 mA cm(-2) for the best performing system. Using photoluminescence (PL) quenching and transient charge extraction techniques, we quantify geminate and nongeminate losses and find that fewer excitons reach the donor-acceptor interface in polymers with further away branching points due to larger aggregate sizes. In these material systems, the photogeneration is therefore mainly limited by exciton harvesting efficiency. The authors acknowledge support by the German Excellence Initiative via the Cluster of Excellence EXC 1056 "Center for Advancing Electronics Dresden" (cfaed). For the GIWAXS measurements, the authors acknowledge KMC-2 diffraction beamline of the Photon source BESSY-II, Helmholtz Zentrum Berlin. Additionally, for TEM microscopy, the authors acknowledge Dr. Petr Formanek from the Leibniz-Institut fur Polymerforschung Dresden. T.E. acknowledges support by the German Alexander von Humboldt foundation. J.B., S.U., and K.V. acknowledge support from the German Federal Ministry for Education and Research (BMBF) through the InnoProfile Projekt "Organische p-i-n Bauelemente 2.2" (03IPT602X). Furthermore, S.U. acknowledges support by the graduate academy of the TU Dresden, financed by the excellence initiative of the German federal and state governments. E.C.-F. and U.H. and D.N. acknowledge funding by the BMBF (UNVEIL, FKZ 13N13719) and the DFG (SFB 951 "HIOS").

The best performing organic solar cells (OSC) efficiently absorb photons and convert them to free charge carriers, which are subsequently collected at the electrodes. However, the energy lost in this process is much larger than for inorganic and perovskite solar cells, currently limiting the power conversion efficiency of OSCs to values slightly below 14%. To quantify energy losses, the open-circuit voltage of the solar cell is often compared to its optical gap. The latter is, however, not obvious to determine for organic materials which have broad absorption and emission bands, and is often done erroneously. Nevertheless, a deeper understanding of the energy loss mechanisms depends crucially on an accurate determination of the energies of the excited states involved in the photo-conversion process. This perspective therefore aims to summarize how the optical gap can be precisely determined, and how it relates to energy losses in organic photovoltaic materials. This work received funding from the German Federal Ministry for Education and Research (BMBF) through the InnoProle Projekt “Organische p–i–n Bauelemente 2.2” (03IPT602X).

We have designed a small molecule based on benzothiadiazole-triphenylamine moieties (BTD-TPA(2)), composed of an electron-poor benzothiadiazole core with two electron-rich triphenylamine arms. BTD-TPA(2) was synthesized in a facile manner using a Suzuki cross-coupling reaction. The molecule was rationally designed to take advantage of the synergistic effect of BTD, which allows the formation of a favorable band gap material, and triphenylamine (TPA) moieties, which favour efficient hole extraction and transport properties. A thin layer of BTD-TPA(2) was placed between the photo-active DBP/C-70 layer stack and the MoOx electrical contact. With an optimized interlayer thickness of 35 nm, the attained photovoltaic properties were substantially superior to those of the reference devices. This has its origin in the dual functionality of BTD-TPA(2), i.e., efficient exciton blocking and improved hole extraction at the anode contact. The obtained results led to an improved power conversion efficiency of 5.66% for a vacuum deposited bilayer DBP/C-70 solar cell, which will be the new state of the art for bilayer DBP based solar cells. This project has received funding from the European Union Seventh Framework Programme under grant agreement no. 607232 [THINFACE] and is partially supported by a European Research Council grant [MOLEMAT, 72630], as well as by the German Federal Ministry for Education and Research (BMBF) through the InnoProfille project "Organische p-i-n Bauelemente 2.2' (803IPT602X).

Spectroscopic photodetection plays a key role in many emerging applications such as context-aware optical sensing, wearable biometric monitoring, and biomedical imaging. Photodetectors based on organic semiconductors open many new possibilities in this field. However, ease of processing, tailorable optoelectronic properties, and sensitivity for faint light are still significant challenges. Here, the authors report a novel concept for a tunable spectral detector by combining an innovative transmission cavity structure with organic absorbers to yield narrowband organic photodetection in the wavelength range of 400-1100 nm, fabricated in a full-vacuum process. Benefiting from this strategy, one of the best performed narrowband organic photodetectors is achieved with a finely wavelength-selective photoresponse (full-width-at-half-maximum of approximate to 40 nm), ultrahigh specific detectivity above 10(14) Jones, the maximum response speed of 555 kHz, and a large dynamic range up to 168 dB. Particularly, an array of transmission cavity organic photodetectors is monolithically integrated on a small substrate to showcase a miniaturized spectrometer application, and a true proof-of-concept transmission spectrum measurement is successfully demonstrated. The excellent performance, the simple device fabrication as well as the possibility of high integration of this new concept challenge state-of-the-art low-noise silicon photodetectors and will mature the spectroscopic photodetection into technological realities. China Scholarship CouncilChina Scholarship Council [201706070125, 201706890003, 201706140127]; DFGGerman Research Foundation (DFG)European Commission [VA 1035/5-1]; Sachsische Aufbaubank [100325708]

In disordered organic semiconductors, the transfer of a rather localized charge carrier from one site to another triggers a deformation of the molecular structure quantified by the intramolecular relaxation energy. A similar structural relaxation occurs upon population of intermolecular charge-transfer (CT) states formed at organic electron donor (D)-acceptor (A) interfaces. Weak CT absorption bands for D A complexes occur at photon energies below the optical gaps of both the donors and the C-60 acceptor as a result of optical transitions from the neutral ground state to the ionic CT state. In this work, we show that temperature-activated intramolecular vibrations of the ground state play a major role in determining the line shape of such CT absorption bands. This allows us to extract values for the relaxation energy related to the geometry change from neutral to ionic CT complexes. Experimental values for the relaxation energies of 20 D:C-60 CT complexes correlate with values calculated within density functional theory. These results provide an experimental method for determining the polaron relaxation energy in solid-state organic D-A blends and show the importance of a reduced relaxation energy, which we introduce to characterize thermally activated CT processes. This work was supported by the German Federal Ministry for Education and Research (BMBF) through the InnoProfille project "Organische p-i-n Bauelemente 2.2". F.O. would like to thank the German Research Foundation (DFG) for financial support (Grant OR 349/1). This work was partly supported by the DFG within the Cluster of Excellence "Center for Advancing Electronics Dresden." F.P. and D.N. acknowledge funding by the DFG via the SFB 951 "HIOS". T.V. acknowledges the Agency for Innovation by Science and Technology in Flanders (IWT) for funding his Ph.D. The work at Georgia Tech was supported by the Department of the Navy, Office of Naval Research Award No. N00014-14-1-0580 (CAOP MURI) and through a state-sponsored scholarship for graduate students to Y.F. from the China Scholarship Council. We acknowledge the Center for Information Services and High Performance Computing (ZIH) at TU Dresden for computational resources. We thank Prof. Bauerle from the University of Ulm for the supply of DH4T and DH6T and Markus Hummert for P4-Ph4-DIP and BP-Bodipy.

Strong light-matter coupling can re-arrange the exciton energies in organic semiconductors. Here, we exploit strong coupling by embedding a fullerene-free organic solar cell (OSC) photo-active layer into an optical microcavity, leading to the formation of polariton peaks and a red-shift of the optical gap. At the same time, the open-circuit voltage of the device remains unaffected. This leads to reduced photon energy losses for the low-energy polaritons and a steepening of the absorption edge. While strong coupling reduces the optical gap, the energy of the charge-transfer state is not affected for large driving force donor-acceptor systems. Interestingly, this implies that strong coupling can be exploited in OSCs to reduce the driving force for electron transfer, without chemical or microstructural modifications of the photo-active layer. Our work demonstrates that the processes determining voltage losses in OSCs can now be tuned, and reduced to unprecedented values, simply by manipulating the device architecture., Strong light-matter coupling can tune exciton properties but its effect in photovoltaics remains unexplored. Here Nikolis et al. show that the photon energy loss from optical gap to open-circuit voltage can be reduced to unprecedented values by embedding organic solar cells in optical microcavities.

Organic solar cells are thought to suffer from poor thermal stability of the active layer nanostructure, a common belief that is based on the extensive work that has been carried out on fullerene-based systems. We show that a widely studied non-fullerene acceptor, the indacenodithienothiophene-based acceptor ITIC, crystallizes in a profoundly different way as compared to fullerenes. Although fullerenes are frozen below the glass-transition temperature T-g of the photovoltaic blend, ITIC can undergo a glass-crystal transition considerably below its high T-g of similar to 180 degrees C. Nanoscopic crystallites of a low-temperature polymorph are able to form through a diffusion-limited crystallization process. The resulting fine-grained nanostructure does not evolve further with time and hence is characterized by a high degree of thermal stability. Instead, above T-g, the low temperature polymorph melts, and micrometer-sized crystals of a high-temperature polymorph develop, enabled by more rapid diffusion and hence long-range mass transport. This leads to the same detrimental decrease in photovoltaic performance that is known to occur also in the case of fullerene-based blends. Besides explaining the superior thermal stability of non-fullerene blends at relatively high temperatures, our work introduces a new rationale for the design of bulk heterojunctions that is not based on the selection of high-T-g materials per se but diffusion-limited crystallization. The planar structure of ITIC and potentially other non-fullerene acceptors readily facilitates the desired glass-crystal transition, which constitutes a significant advantage over fullerenes, and may pave the way for truly stable organic solar cells. We acknowledge financial support from the Knut and Alice Wallenberg Foundation through the project "Mastering Morphology for Solution-borne Electronics", the Swedish Research Council (grant agreement no. 2016-06146), and the Swedish Foundation for Strategic Research (grant agreement no. RMA15-0052). We thank the Cornell High Energy Synchrotron Source (CHESS), supported by the NSF under award DMR-1332208, for providing time for GIWAXS measurements. J.B. and K.V. acknowledge funding from the German Federal Ministry for Education and Research (BMBF) through the InnoProfile project "Organische p-i-n Bauelemente 2.2" (03IPT602X).

Achieving long-term stability in organic solar cells is a remaining bottleneck for the commercialization of this otherwise highly appealing technology. In this work, we study the performance and stability differences in standard and inverted DBP/C-70 based organic solar cells. Differences in the charge-transfer state properties of inverted and standard configuration DBP/C-70 solar cells are revealed by sensitive external quantum efficiency measurements, leading to differences in the open-circuit voltages of the devices. The degradation of standard and inverted solar cell configurations at ISOS aging test conditions (ISOS-D-3 and ISOS-T-3) was investigated and compared. The results indicate that the performance drop in the small molecule bilayer solar cells is less related to changes at the D-A interface, suggesting also a pronounced morphological stability, and instead, in the case of inverted cells, dominated by degradation at the electron transport layer (ETL) bathocuproine (BCP). Photoluminescence measurements, electron-only-device characteristics, and stability measurements show improved exciton blocking, electron transport properties and a higher stability for BCP/Ag ETL stacks, giving rise to inverted devices with enhanced performance and device stability. The research leading to these results has received funding from the People Programme (Marie Curie Actions) of the European Union's Seventh Framework Programme FP7/2007-2013/under REA Grant Agreement No. 607232, THINFACE. J.B., D.S. and K.V. acknowledge the German Federal Ministry for Education and Research (BMBF) for funding the project through the InnoProfile project "Organische p-i-n Bauelemente 2.2".

Intermolecular charge-transfer states at the interface between electron donating (D) and accepting (A) materials are crucial for the operation of organic solar cells but can also be exploited for organic light-emitting diodes(1,2). Non-radiative charge-transfer state decay is dominant in state-of-the-art D-A-based organic solar cells and is responsible for large voltage losses and relatively low power-conversion efficiencies as well as electroluminescence external quantum yields in the 0.01-0.0001% range(3,4). In contrast, the electroluminescence external quantum yield reaches up to 16% in D-A-based organic light-emitting diodes(5-7). Here, we show that proper control of charge-transfer state properties allows simultaneous occurrence of a high photovoltaic and emission quantum yield within a single, visible-light-emitting D-A system. This leads to ultralow-emission turn-on voltages as well as significantly reduced voltage losses upon solar illumination. These results unify the description of the electro-optical properties of charge-transfer states in organic optoelectronic devices and foster the use of organic D-A blends in energy conversion applications involving visible and ultraviolet photons(8-11). This work was supported by the German Federal Ministry for Education and Research (BMBF) through the InnoProfile project 'Organische p-i-n Bauelemente 2.2' (03IPT602X) and by the German Research Foundation (DFG) project Photogen (VA 1035/5-1). X.J. and Y.L. acknowledge support from the China Scholarship Council (nos. 201706140127 and 201506920047, respectively). The authors also acknowledge the DFG for supporting K.T. (project 382633022 'RECOLPER'), F.P., S.Ro. and D.N. (SFB 951 'HIOS') and A.F. (RE 3198/6-1 'EFOD').

Efficient charge generation in organic semiconductors usually requires an interface with an energetic gradient between an electron donor and an electron acceptor in order to dissociate the photogenerated excitons. However, single-component organic solar cells based on chloroboron subnaphthalocyanine (SubNc) have been reported to provide considerable photocurrents despite the absence of an energy gradient at the interface with an acceptor. In this work, it is shown that this is not due to direct free carrier generation upon illumination of SubNc, but due to a field-assisted exciton dissociation mechanism specific to the device configuration. Subsequently, the implications of this effect in bilayer organic solar cells with SubNc as the donor are demonstrated, showing that the external and internal quantum efficiencies in such cells are independent of the donor-acceptor interface energetics. This previously unexplored mechanism results in efficient photocurrent generation even though the driving force is minimized and the open-circuit voltage is maximized. V.C.N. and Y.D. contributed equally to this work. The authors would like to thank Prof. Dr. Dieter Neher for providing measurement time on the electroluminescence setup of his lab at University of Potsdam. They would also like to acknowledge the Optoelectronics group in the University of Cambridge for sharing the global analysis codes. This work was supported by the German Federal Ministry of Education and Research (BMBF) through the InnoProfile project "Organische p-i-n Bauelemente2.2" (FKZ 03IPT602X). A.A.B. is a Royal Society university research fellow. Open access funding enabled and organized by Projekt DEAL. Nikolis, VC (corresponding author), Tech Univ Dresden, Dresden Integrated Ctr Appl Phys & Photon Mat IAP, Nothnitzer Str 61, D-01187 Dresden, Germany ; Tech Univ Dresden, Inst Appl Phys, Nothnitzer Str 61, D-01187 Dresden, Germany. Bakulin, AA (corresponding author), Imperial Coll London, Mol Sci Res Hub, London W12 0BE, England. Vandewal, K (corresponding author), Hasselt Univ, Inst Mat Res IMO IMOMEC, Wetenschapspk 1, B-3590 Diepenbeek, Belgium. vasileios_christos.nikolis1@tu-dresden.de; a.bakulin@imperial.ac.uk; koen.vandewal@uhasselt.be

Organic solar cells with an electron donor diluted in a fullerene matrix have a reduced density of donor-fullerene contacts, resulting in decreased free-carrier recombination and increased open-circuit voltages. However, the low donor concentration prevents the formation of percolation pathways for holes. Notwithstanding, high (>75%) external quantum efficiencies can be reached, suggesting an effective hole-transport mechanism. Here, we perform a systematic study of the hole mobilities of 18 donors, diluted at similar to 6 mol % in C-60, with varying frontier energy level offsets and relaxation energies. We find that hole transport between isolated donor molecules occurs by long-range tunneling through several fullerene molecules, with the hole mobilities being correlated to the relaxation energy of the donor. The transport mechanism presented in this study is of general relevance to bulk heterojunction organic solar cells where mixed phases of fullerene containing a small fraction of a donor material or vice versa are present as well. The work was funded by the German Federal Ministry for Education and Research (BMBF) through the InnoProfile Projekt "Organische p-i-n Bauelemente 2.2" (03IPT602X). This work was supported by the Deutsche Forschungsgemeinschaft (project OR 349/1-1), by the Department of the Navy, Office of Naval Research Award No. N00014-14-1-0580 (CAOP MUM), by the German Ministry of Science and Education (BMBF), project UNVEiL, and through a state sponsored scholarship for graduate students to Y.F. from the China Scholarship Council. M.N. acknowledges funding from "Svenska Tekniska Vetenskapsakademien i Finland". Grants for computing time from the Center for Information Services and High Performance Computing (ZIH) are gratefully acknowledged.

Fermi level control by doping is established since decades in inorganic semiconductors and has been successfully introduced in organic semiconductors. Despite its commercial success in the multi-billion OLED display business, molecular doping is little understood, with its elementary steps controversially discussed and mostly-empirical-materials design. Particularly puzzling is the efficient carrier release, despite a presumably large Coulomb barrier. Here we quantitatively investigate doping as a two-step process, involving single-electron transfer from donor to acceptor molecules and subsequent dissociation of the ground-state integer-charge transfer complex (ICTC). We show that carrier release by ICTC dissociation has an activation energy of only a few tens of meV, despite a Coulomb binding of several 100 meV. We resolve this discrepancy by taking energetic disorder into account. The overall doping process is explained by an extended semiconductor model in which occupation of ICTCs causes the classically known reserve regime at device-relevant doping concentrations., Molecular doping is routinely used in organic semiconductor devices nowadays, but the physics at play remains unclarified. Tietze et al. describe it as a two-step process and show it costs little, energetically, to dissociate charge transfer complexes due to energetic disorder of organic semiconductors.

Blending organic electron donors and acceptors yields intermolecular charge-transfer states with additional optical transitions below their optical gaps. In organic photovoltaic devices, such states play a crucial role and limit the operating voltage. Due to its extremely weak nature, direct intermolecular charge-transfer absorption often remains undetected and unused for photocurrent generation. Here, we use an optical microcavity to increase the typically negligible external quantum efficiency in the spectral region of charge-transfer absorption by more than 40 times, yielding values over 20%. We demonstrate narrowband detection with spectral widths down to 36 nm and resonance wavelengths between 810 and 1,550 nm, far below the optical gap of both donor and acceptor. The broad spectral tunability via a simple variation of the cavity thickness makes this innovative, flexible and potentially visibly transparent device principle highly suitable for integrated low-cost spectroscopic near-infrared photodetection., Interfaces of organic donor-acceptor blends provide intermolecular charge-transfer states with red-shifted but weak absorption. By introducing an optical micro-cavity; Siegmund et al., enhance their photoresponse to achieve narrowband NIR photodetection with broad spectral tunability.

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.

In organic solar cells continuous donor and acceptor networks are considered necessary for charge extraction, whereas discontinuous neat phases and molecularly mixed donor–acceptor phases are generally regarded as detrimental. However, the impact of different levels of domain continuity, purity, and donor–acceptor mixing on charge transport remains only semiquantitatively described. Here, cosublimed donor–acceptor mixtures, where the distance between the donor sites is varied in a controlled manner from homogeneously diluted donor sites to a continuous donor network are studied. Using transient measurements, spanning from sub-picoseconds to microseconds photogenerated charge motion is measured in complete photovoltaic devices, to show that even highly diluted donor sites (5.7%–10% molar) in a buckminsterfullerene matrix enable hole transport. Hopping between isolated donor sites can occur by long-range hole tunneling through several buckminsterfullerene molecules, over distances of up to ≈4 nm. Hence, these results question the relevance of “pristine” phases and whether a continuous interpenetrating donor–acceptor network is the ideal morphology for charge transport. Funding agencies: German Federal Ministry for Education and Research (BMBF) through the InnoProfille project "Organische p-i-n Bauelemente 2.2"; Research Council of Lithuania [MIP-85/2015]; Science Council of Sweden; Knut and Alice Wallenberg foundation; Wallenberg Scholar

The nanoscale morphology of the bulk heterojunction absorber layer in an organic solar cell (OSC) is of key importance for its efficiency. The morphology of high performance vacuum-processed, small molecule OSCs based on oligothiophene derivatives (DCV5T-Me) blended with C60 on various length scales is studied. The analytical electron microscopic techniques such as scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, highly sensitive external quantum efficiency measurements, and meso and nanoscale simulations are employed. Unique insights into the relation between processing, morphology, and efficiency of the final devices are obtained. It is shown that the connectivity of the oligothiophene-C60 network is independent of the material domain size. The decisive quantity controlling the internal quantum efficiency is the energetic disorder induced by material mixing, strongly limiting charge and exciton transport in the OSCs.

Conjugated polymers and small molecules based on alternating electron-donating (D) and electronaccepting (A) building blocks have led to state-of-the-art organic solar cell materials governing efficiencies beyond 10%. Unfortunately, the connection of D and A building blocks via cross-coupling reactions does not always proceed as planned, which can result in the generation of side products containing D-D or A-A homocoupling motifs. Previous studies have reported a reduced performance in polymer and small molecule solar cells when such defect structures are present. A general consensus on the impact of homocouplings on device performance is, however, still lacking as is a profound understanding of the underlying causes of the device deterioration. For differentiating the combined effect of molecular weight and homocouplings in polymer solar cells, a systematic study on a small molecule system (DTS(FBBTh2)2) is presented. The impact of homocouplings on nanomorphology, thermal, and electro-optical properties is investigated. It is demonstrated that small quantities of homocouplings (