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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.

Organic photovoltaics (PV) is an energy-harvesting technology that offers many advantages, such as flexibility, low weight and cost, as well as environmentally benign materials and manufacturing techniques. Despite growth of power conversion efficiencies to around 19 % in the last years, organic PVs still lag behind inorganic PV technologies, mainly due to high losses in open-circuit voltage. Understanding and improving open circuit voltage in organic solar cells is challenging, as it is controlled by the properties of a donor-acceptor interface where the optical excitations are separated into charge carriers. Here, we provide an electrostatic model of a rough donor-acceptor interface and test it experimentally on small molecule PV materials systems. The model provides concise relationships between the open-circuit voltage, photovoltaic gap, charge-transfer state energy, and interfacial morphology. In particular, we show that the electrostatic bias generated across the interface reduces the photovoltaic gap. This negative influence on open-circuit voltage can, however, be circumvented by adjusting the morphology of the donor-acceptor interface. Organic solar cells, despite their high power conversion efficiencies, suffer from open circuit voltage losses making them less appealing in terms of applications. Here, the authors, supported with experimental data on small molecule photovoltaic cells, relate open circuit voltage to photovoltaic gap, charge-transfer state energy, and donor-acceptor interfacial morphology. Open Access funding enabled and organized by Projekt DEAL. This publication is based on work supported by the KAUST Office of Sponsored Research (OSR) under award nos. OSR-2018-CARF/CCF-3079 and OSR-CRG2018- 3746. D.A. also acknowledges the KAUST PSE Division for hosting his sabbatical in the framework of the Division’s Visiting Faculty program. D.A. acknowledges funding by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) for financial support through the collaborative research centers TRR 146, SPP 2196, and grant number 460766640. We thank Kun-Han Lin, Leanne Paterson, Wenlan Liu, Mukunda Mandal, and Naomi Kinaret for fruitful discussions and proof reading of the manuscript. Furthermore, the authors acknowledge Dr. Beatrice Beyer from Fraunhofer Institut FEP for supplying the donor molecule ZnF4Pc. J.B. and K.L. acknowledge the German Federal Ministry of Education and Research (BMBF) for funding through the projects “Pergamon” (16ME0012) and “Flexmonirs” (01DR20008A).

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.

Blending organic molecules to tune their energy levels is currently being investigated as an approach to engineer the bulk and interfacial optoelectronic properties of organic semiconductors. It has been proven that the ionization energy and electron affinity can be equally shifted in the same direction by electrostatic effects controlled by blending similar halogenated derivatives with different energetics. Here we show that the energy gap of organic semiconductors can also be tuned by blending. We use oligothiophenes with different numbers of thiophene rings as an example and investigate their structure and electronic properties. Photoelectron spectroscopy and inverse photoelectron spectroscopy show tunability of the single-particle gap, with the optical gaps showing similar, but smaller, effects. Theoretical analysis shows that this tuning is mainly caused by a change in the dielectric constant with blend ratio. Further studies will explore the practical impact of this energy-level engineering strategy for optoelectronic devices.

Interfacial layers in conjunction with suitable charge-transport layers can significantly improve the performance of optoelectronic devices by facilitating efficient charge carrier injection and extraction. This work uses a neat C60 interlayer on the anode to experimentally reveal that surface recombination is a significant contributor to nonradiative recombination losses in organic solar cells. These losses are shown to proportionally increase with the extent of contact between donor molecules in the photoactive layer and a molybdenum oxide (MoO3) hole extraction layer, proven by calculating voltage losses in low- and high-donor-content bulk heterojunction device architectures. Using a novel in-device determination of the built-in voltage, the suppression of surface recombination, due to the insertion of a thin anodic-C60 interlayer on MoO3, is attributed to an enhanced built-in potential. The increased built-in voltage reduces the presence of minority charge carriers at the electrodes-a new perspective on the principle of selective charge extraction layers. The benefit to device efficiency is limited by a critical interlayer thickness, which depends on the donor material in bilayer devices. Given the high popularity of MoO3 as an efficient hole extraction and injection layer and the increasingly popular discussion on interfacial phenomena in organic optoelectronic devices, these findings are relevant to and address different branches of organic electronics, providing insights for future device design.

A comprehensive study of the optical properties of CsPbBr

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.

Efficient exciton dissociation and subsequent generation of free charge carriers at the organic donor-acceptor interface requires a number of electron-transfer processes. It is a common view that these steps result in an unavoidable energy loss in organic photovoltaic devices that is not present in other types of solar cells. The currently best performing organic solar cells with power conversion efficiencies over 16% challenge this view, and no interfacial charge-transfer states with energy significantly lower than the strongly absorbing singlet states are detected within the gap of the used donor and acceptor materials. This Perspective will discuss implications, the remaining sources of energy loss, and open questions to be solved to achieve power conversion efficiencies over 20%.

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.

An understanding of the factors limiting the open-circuit voltage (V-oc) and related photon energy loss mechanisms is critical to increase the power conversion efficiency (PCE) of small-molecule organic solar cells (OSCs), especially those with near-infrared (NIR) absorbers. In this work, two NIR boron dipyrromethene (BODIPY) molecules are characterized for application in planar (PHJ) and bulk (BHJ) heterojunction OSCs. When two H atoms are substituted by F atoms on the peripheral phenyl rings of the molecules, the molecular aggregation type in the thin film changes from the H-type to J-type. For PHJ devices, the nonradiative voltage loss of 0.35 V in the J-aggregated BODIPY is lower than that of 0.49 V in the H-aggregated device. In BHJ devices with a nonradiative voltage loss of 0.35 V, a PCE of 5.5% is achieved with an external quantum efficiency (EQE) maximum of 68% at 700 nm.

The involvement of charge-transfer (CT) states in the photogeneration and recombination of charge carriers has been an important focus of study within the organic photovoltaic community. In this work, we investigate the molecular factors determining the mechanism of photocurrent generation in low-donor-content organic solar cells, where the active layer is composed of vacuum-deposited C

Extraction barriers are usually undesired in organic semiconductor devices since they lead to reduced device performance. In this work, we intentionally introduce an extraction barrier for holes, leading to nonlinear photoresponse. The effect is utilized in near-infrared (NIR) organic photodetectors (OPDs) to perform distance measurements, as delineated in the focus-induced photoresponse technique (FIP). The extraction barrier is introduced by inserting an anodic interlayer with deeper highest occupied molecular orbital (HOMO), compared to the donor material, into a well-performing OPD. With increasing irradiance, achieved by decreasing the illumination spot area on the OPD, a higher number of holes pile up at the anode, counteracting the built-in field and increasing charge-carrier recombination in the bulk. This intended nonlinear response of the photocurrent to the irradiance allows determining the distance between the OPD and the light source. We demonstrate fully vacuum-deposited organic NIR optical distance photodetectors with a detection area up to 256 mm2 and detection wavelengths at 850 and 1060 nm. Such NIR OPDs have a high potential for precise, robust, low-cost, and simple optical distance measurement setups.

Interfacial layers in conjunction with suitable charge-transport layers can significantly improve the performance of optoelectronic devices by facilitating efficient charge carrier injection and extraction. This work uses a neat C

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.

Interfaces between organic electron-donating (D) and electron-accepting (A) materials can show efficient free charge carrier generation upon illumination, enabling organic photovoltaic devices and photodetectors with photon to electron conversion yields approaching 100%. Recently, organic light-emitting diodes (OLEDs) based on charge transfer (CT) (or exciplex) emission occurring at such D-A interfaces have been shown to exhibit high electroluminescence external quantum yields (EQEEL). However, no organic D-A combination with both a high EQEEL, as well as a high free carrier generation yield has been discovered so far. Such a system would result in significantly higher operating voltages in organic solar cells, reduced dark current in organic photodetectors, and reduced driving voltages for OLEDs.

Blending organic molecules to tune their energy levels is currently being investigated as an approach to engineer the bulk and interfacial optoelectronic properties of organic semiconductors. It has been proven that the ionization energy and electron affinity can be equally shifted in the same direction by electrostatic effects controlled by blending similar halogenated derivatives with different energetics. Here we show that the energy gap of organic semiconductors can also be tuned by blending. We use oligothiophenes with different numbers of thiophene rings as an example and investigate their structure and electronic properties. Photoelectron spectroscopy and inverse photoelectron spectroscopy show tunability of the single-particle gap, with the optical gaps showing similar, but smaller, effects. Theoretical analysis shows that this tuning is mainly caused by a change in the dielectric constant with blend ratio. Further studies will explore the practical impact of this energy-level engineering strategy for optoelectronic 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

Highly responsive organic photodetectors allow a plethora of applications in fields like imaging, health, security monitoring, etc. Photomultiplication-type organic photodetectors (PM-OPDs) are a desirable option due to their internal amplification mechanism. However, for such devices, significant gain and low dark currents are often mutually excluded since large operation voltages often induce high shot noise. Here, a fully vacuum-processed PM-OPD is demonstrated using trap-assisted electron injection in BDP-OMe:C

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).

Three furan-fused BODIPYs were synthesized with perfluorinated methyl, ethyl and n-propyl groups on the meso-carbon. They were obtained with high yields by reacting the furan-fused 2-carboxylpyrrole in corresponding perfluorinated acid and anhydride. With the increase in perfluorinated alkyl chain length, the molecular packing in the single crystal is influenced, showing increasing stacking distance and decreasing slope angle. All the BODIPYs were characterized as intense absorbers in near infrared region in solid state, peaking at similar to 800 nm with absorption coefficient of over 280 000 cm(-1). Facilitated by high thermal stability, the furan-fused BODIPYs were employed in vacuum-deposited organic solar cells as electron donors. All devices exhibit PCE over 6.0% with the EQE maximum reaching 70% at similar to 790 nm. The chemical modification of the BODIPY donors have certain influence on the active layer morphology, and the highest PCE of 6.4% was obtained with a notably high jsc of 13.6 mA cm(-2). Sensitive EQE and electroluminance studies indicated that the energy losses generated by the formation of a charge transfer state and the radiative recombination at the donor-acceptor interface were comparable in the range of 0.14-0.19 V, while non-radiative recombination energy loss of 0.38 V was the main energy loss route resulting in the moderate V-oc of 0.76 V.

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]

We present organic near-infrared photodetectors based on the absorption of charge-transfer (CT) states at the zinc-phthalocyanine–C60 interface. By using a resonant optical cavity device architecture, we achieve a narrowband detection, centered around 1060 nm and well below (>200 nm) the optical gap of the neat materials. We measure transient photocurrent responses at wavelengths of 532 and 1064 nm, exciting dominantly the neat materials or the CT state, respectively, and obtain rise and fall times of a few nanoseconds at short circuit, independent of the excitation wavelength. The current transients are modeled with time-dependent drift-diffusion simulations of electrons and holes which reconstruct the photocurrent signal, including capacitance and series resistance effects. The hole mobility of the donor material is identified as the limiting factor for the high-frequency response. With this knowledge, we demonstrate a new device concept, which balances hole and electron extraction times and achieves a ...

Organic spectrometers are attractive for biomedicine and industrial process monitoring but are currently limited in terms of spectral selectivity and the accessible wavelength range. Here, we achieve narrowband enhancement of the below-gap near-infrared response of charge-transfer (CT) excitations in organic photodiodes by introducing them into a high-quality microcavity. The device architecture includes a nonconductive distributed Bragg reflector and thin metal electrodes, leading to the formation of sharp Tamm plasmon-polariton resonances. We demonstrate how to tailor the arising multimode spectra for spectroscopic photodetectors and present efficient single-resonance devices with remarkable line widths below 22 nm, which are partially transparent for visible wavelengths. Taking advantage of the spectrally broad CT band, we vary the resonator thickness to provide a proof of concept that benefits from the spectral selectivity of our high-quality microcavities. Finally, utilizing transfer-matrix calculati...

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').

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 C-60 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 (>0.34V). (C) 2016 Published by Elsevier B.V.

Organic materials for near-infrared (NIR) photodetection are in the focus for developing organic optical-sensing devices. The choice of materials for bulk-type organic photodetectors is limited due to effects like high nonradiative recombination rates for low-gap materials. Here, an organic Schottky barrier photodetector with an integrated plasmonic nanohole electrode is proposed, enabling structure-dependent, sub-bandgap photodetection in the NIR. Photons are detected via internal photoemission (IPE) process over a metal/organic semiconductor Schottky barrier. The efficiency of IPE is improved by exciting localized surface plasmon resonances, which are further enhanced by coupling to an out-of-plane Fabry–Perot cavity within the metal/organic/metal device configuration. The device allows large on/off ratio (>1000) and the selective control of individual pixels by modulating the Schottky barrier height. The concept opens up new design and application possibilities for organic NIR photodetectors.

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.

Organic solar cells are a promising technology for a large area conversion of sunlight into electricity. In particular for solar cells based on oligomers (small molecules), efficient donor materials absorbing wavelengths larger than 780 nm are still rare. Here, we investigate three aza-BODIPY dyes absorbing in the infrared. The addition of side groups leads to a red shift of the optical gap from 802 to 818 nm. In optimized devices using these donors in a bulk heterojunction with C-60, we observe a higher charge carrier mobility and a higher power conversion efficiency for the molecules without a methyl or methoxy side group lowering the molecular reorganization energy. Surprisingly, the donor-acceptor blend with the lowest energy loss during the electron transfer to the C-60 yields the highest short circuit current. With increasing size of the attached side chain, the devices exhibit a larger trap density, measured by impedance spectroscopy. Based on the investigation of different blend ratios, we conclude that these traps are mainly present in the donor phase. (C) 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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.