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Encapsulated organic solar cells often show a burn-in behaviour under illumination. This burn-in manifests itself as a rapid performance loss followed by a much slower progression of the degradation. Here we investigate the burn-in for PCDTBT:PC70BM solar cells under a wide range of illumination intensities. We find that increasing the sunlight concentration from 1 Sun to up to 100 Suns does not change the degradation behaviour, i.e. the dependence of all principal photovoltaic parameters on the dose of solar exposure (in Sun hours). This suggests that the degradation mechanisms under solar concentration (≤100 Suns) are the same as those observed under 1 Sun. This result makes it possible to use concentrated sunlight for accelerated stability assessment of these devices. We also find that devices with PEDOT:PSS as hole transport material show a rapid drop in open-circuit voltage of around 100 mV during the first Sun hour of light exposure. By replacing PEDOT:PSS with MoO3 this initial process can be prevented and only the much slower part of the photo-degradation takes place.

We present an overview of opto-electronic characterization techniques for solar cells including light-induced charge extraction by linearly increasing voltage, impedance spectroscopy, transient photovoltage, charge extraction and more. Guidelines for the interpretation of experimental results are derived based on charge drift-diffusion simulations of solar cells with common performance limitations. It is investigated how nonidealities like charge injection barriers, traps and low mobilities among others manifest themselves in each of the studied cell characterization techniques. Moreover, comprehensive parameter extraction for an organic bulk-heterojunction solar cell comprising PCDTBT:PC70BM is demonstrated. The simulations reproduce measured results of 9 different experimental techniques. Parameter correlation is minimized due to the combination of various techniques. Thereby a route to comprehensive and accurate parameter extraction is identified.

There is increasing evidence that the presence of mobile ions in perovskite solar cells can cause a current-voltage curve hysteresis. However, it is still subject of ongoing debates how exactly mobile ions influence the device operation. We use drift-diffusion simulations incorporating mobile ions to describe IV-curves of preconditioned methylammonium lead iodide perovskite solar cells and compare them with experimental results. Our simulation results show that the hysteresis depends on the extent of surface recombination and on the diffusion length of charge carriers. We provide a detailed explanation for the reduced hysteresis of perovskite solar cells with high power conversion efficiencies. We find that in high-efficiency solar cells ion migration is still present, but does not cause a hysteresis effect. In these devices charge extraction is mainly driven by diffusion of free electrons and holes.

If not oriented perfectly isotropically, the strong dipole moment of polar organic semiconductor materials such as tris-(8-hydroxyquinolate)aluminum (Alq3) will lead to the buildup of a giant surface potential (GSP) and thus to a macroscopic dielectric polarization of the organic film. Despite this having been a known fact for years, the implications of such high potentials within an organic layer stack have only been studied recently. In this work, the influence of the GSP on hole injection into organic layers is investigated. Therefore, we apply a concept called dipolar doping to devices consisting of the prototypical organic materials N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) as nonpolar host and Alq3 as dipolar dopant with different mixing ratios to tune the GSP. The mixtures are investigated in single-layer monopolar devices as well as bilayer metal/insulator/semiconductor structures. Characterization is done electrically using current-voltage (I-V) characteristics, impedance spectroscopy, and charge extraction by linearly increasing voltage and time of flight, as well as with ultraviolet photoelectron spectroscopy. We find a maximum in device performance for moderate to low doping concentrations of the polar species in the host. The observed behavior can be described on the basis of the Schottky effect for image-force barrier lowering, if the changes in the interface dipole, the carrier mobility, and the GSP induced by dipolar doping are taken into account.

Many electron transport layer materials (ETL) employed in state of the art organic light emitting diodes (OLEDs) are known to be polar. We combine for the first time simulations and electrical characterization of OLEDs based on polar ETL, in order to understand the impact of such materials on the device operation. Depending on the orientation of the dipole orientation, simulations predict either a benefit or a disadvantage of the polar ETL for the device performance.

We report a cooperative study conducted between different laboratories to investigate organic solar cell degradation with respect to P3HT material properties and different solar cell architectures. Various batches of P3HT were collected from different suppliers reflecting commercial availability as well as properties variability. Among the materials properties explicitly considered were the molar mass, dispersity, regio-regularity, impurities by trace metals and intrinsic doping evaluated from radical concentrations. Each of the participating laboratories contributing test devices applied their own layer stack, i.e. their own device architecture and layout. This variation was appreciated as another parameter for evaluation. Even though a large amount of devices failed due to extrinsic degradation effects, indeed, some materials properties were found to be more important than others for obtaining long lifetimes and high stability of P3HT-based polymer solar cells., All authors are grateful for support from COST Action MP 1307, “StableNextSol”. This article is based upon work from COST Action StableNextSol project MP1307, supported by COST (European Cooperation in Science and Technology). RM, TF, DF, RR and HH are grateful for financial support within the frame of “AIMS in OPV” junior research group by the BMBF, Germany. L.C. is thankful to ENEA (Ente Nazionale Energia e Ambiente) and the Italian Ministry of Foreign Affairs for a visitor post-doc fellowship to BGU. FG and MD are grateful for financial support by the National Center for Research and Development within the Project POSCIS under Grant No. LIDER/09/129/L-3/11/NCBR/2012). IVF and EAK acknowlegde financial support from Adelis Foudation. N. Blaubach is acknowledged for ICP measurements. MP thanks the Bundesministerium für Bildung und Forschung, Germany (BMBF FKZ 03EK3507).

​This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acsami.9b04991, A variety of experiments on vacuum-deposited methylammonium lead iodide perovskite solar cells are presented, including JV curves with different scan rates, light intensity-dependent open-circuit voltage, impedance spectra, intensity-modulated photocurrent spectra, transient photocurrents, and transient voltage step responses. All these experimental data sets are successfully reproduced by a charge drift-diffusion simulation model incorporating mobile ions and charge traps using a single set of parameters. While previous modeling studies focused on a single experimental technique, we combine steady-state, transient, and frequency-domain simulations and measurements. Our study is an important step toward quantitative simulation of perovskite solar cells, leading to a deeper understanding of the physical effects in these materials. The analysis of the transient current upon voltage turn-on in the dark reveals that the charge injection properties of the interfaces are triggered by the accumulation of mobile ionic defects. We show that the current rise of voltage step experiments allow for conclusions about the recombination at the interface. Whether one or two mobile ionic species are used in the model has only a minor influence on the observed effects. A delayed current rise observed upon reversing the bias from +3 to -3 V in the dark cannot be reproduced yet by our drift-diffusion model. We speculate that a reversible chemical reaction of mobile ions with the contact material may be the cause of this effect, thus requiring a future model extension. A parameter variation is performed in order to understand the performance-limiting factors of the device under investigation.

Many electron transport layer materials (ETL) employed in state of the art organic light emitting diodes (OLEDs) are known to be polar. We combine for the first time simulations and electrical characterization of OLEDs based on polar ETL, in order to understand the impact of such materials on the device operation. Depending on the orientation of the dipole orientation, simulations predict either a benefit or a disadvantage of the polar ETL for the device performance. We also show that OLEDs featuring a polar material are perfectly suited for extracting mobility activation energy and Injection barrier from the anode to the ETL.

Charge carrier transport in organic semiconductor devices is thermally activated with characteristic activation energies in the range of 0.2–0.6 eV, leading to strongly temperature-dependent behaviour. For designing efficient organic semiconductor materials and devices, it is therefore indispensable to understand the origin of these activation energies. We propose that in bilayer organic light-emitting diodes (OLEDs) employing a polar electron transport layer, as well as in metal-insulator-semiconductor (MIS) devices, the hole injection barrier Einj and the hole mobility activation energy Eμ can be decoupled from each other if temperature-dependent capacitance-frequency (C-f-T) and MIS-CELIV (charge extraction by linearly increasing voltage) experiments are combined. While the C-f-T signal contains information of both injection and transport, the CELIV current is expected to be insensitive to the electrode injection properties. We employ numerical drift-diffusion simulations to investigate the accuracy of...

Article 1800474 Appreciable progress has been achieved in the development of organic photovoltaics (OPV) over the last decade. However, further improvement of operational stability remains a challenge. In this contribution, focus is placed on corrosion and delamination of the metal contact, which are mainly caused by oxygen or water vapor ingress but in other cases also via mechanical wear and different thermal expansion coefficients. So‐called pinholes and electrode edges provide pathways for ingress of water vapor and oxygen, which may attack the metal–organic interface. Thus, electrical insolation via formation of insulating metal oxide and concomitant mechanical delamination occurs. As charge injection and extraction is suppressed at insulated and delaminated areas, the active area contributing to power conversion gets reduced. This work links analytical and numerical predictions about the active area in contact with the electrode to experimentally observe dependencies. Spatially and time‐resolved electroluminescence measurements provide information on location, size, and growth‐rate of insulated areas. Area loss rates for dark spots depend either sub‐linear (for early stages and edge‐ingress) or linear (later stages) on time. The initial defect size has a clear impact on growth rates. Furthermore, it has possible to demonstrate titanium oxide interlayers to slow down this type of extrinsic degradation.

Single-carrier devices are an excellent model system to study charge injection and charge transport properties of (doped) transport layers and to draw conclusions about organic electronics devices in which they are used. By combining steady-state and impedance measurements at varying temperatures of hole-only devices with different intrinsic layer thicknesses, we are able to determine all relevant material parameters, such as the charge mobility and the injection barrier. Furthermore, the correlation and sensitivity analyses reveal that the proposed approach to study these devices is especially well suited to extract the effective doping density, a parameter which cannot be easily determined otherwise. The effective doping density is crucial in organic light-emitting diodes (OLEDs) for realizing efficient injection, charge balance, and lateral conductivity in display or lighting applications. With the fitted drift-diffusion device model, we are further able to explain the extraordinary two-plateau capacitance–frequency curve of these hole-only devices, which originates from charges that flow into the intrinsic layer at zero applied offset voltage. We demonstrate that the observation of this behaviour is a direct indication for ideal charge injection properties and the observed capacitance–frequency feature is linked to the charge carrier mobility in the intrinsic layer. The extracted material parameters may directly be used to simulate and optimize full OLED devices employing the investigated hole-injection and -transport materials.

We present a significant efficiency enhancement of hybrid bulk heterojunction solar cells by utilizing CdSe quantum dots attached to reduced graphene oxide (rGO) as the electron accepting phase, blended with the PCPDTBT polymer. The quantum dot attachment to rGO was achieved following a self-assembly approach, recently developed, using thiolated reduced graphene oxide (TrGO) to form a TrGO-CdSe nanocomposite. Therefore, we are able to obtain TrGO-CdSe quantum dot/PCPDTBT bulk-heterojunction hybrid solar cells with power conversion efficiencies of up to 4.2%, compared with up to 3% for CdSe quantum dot/PCPDTBT devices. The improvement is mainly due to an increase of the open-circuit voltage from 0.55 V to 0.72 V. We found evidence for a significant change in the heterojunction donor-acceptor blend nanomorphology, observable by a more vertical alignment of the TrGO-quantum dot nanocomposites in the z-direction and a different nanophase separation in the x-y direction compared to the quantum dot only containing device. Moreover, an improved charge extraction and trap state reduction were observed for TrGO containing hybrid solar cells.

We demonstrate the application of the CELIV (charge carrier extraction by linearly increasing voltage) technique to bilayer organic light-emitting devices (OLEDs) in order to selectively determine the hole mobility in N,N0-bis(1-naphthyl)-N,N0-diphenyl-1,10-biphenyl-4,40-diamine (α-NPD). In the CELIV technique, mobile charges in the active layer are extracted by applying a negative voltage ramp, leading to a peak superimposed to the measured displacement current whose temporal position is related to the charge carrier mobility. In fully operating devices, however, bipolar carrier transport and recombination complicate the analysis of CELIV transients as well as the assignment of the extracted mobility value to one charge carrier species. This has motivated a new approach of fabricating dedicated metal-insulator-semiconductor (MIS) devices, where the extraction current contains signatures of only one charge carrier type. In this work, we show that the MIS-CELIV concept can be employed in bilayer polar OLEDs as well, which are easy to fabricate using most common electron transport layers (ETLs), like Tris-(8-hydroxyquinoline)aluminum (Alq3). Due to the macroscopic polarization of the ETL, holes are already injected into the hole transport layer below the built-in voltage and accumulate at the internal interface with the ETL. This way, by a standard CELIV experiment only holes will be extracted, allowing us to determine their mobility. The approach can be established as a powerful way of selectively measuring charge mobilities in new materials in a standard device configuration.

Organic light-emitting diodes (OLEDs) rely on the use of functional materials with suitable energy levels and mobilities for selective charge carrier injection and transport of one species only at the respective electrode. Until recently, however, the dipolar nature of many organic semiconductors has been largely ignored in this context. In particular, electron transports layers (ETLs) often exhibit spontaneous orientation polarization leading to interfacial charges that modify the electrical potential landscape inside a hetero-layer device. Here we demonstrate that the effect of polar ETLs can be simulated using the well-established Poisson and drift-diffusion formalism, if these interfacial charges are taken into account. Impedance spectroscopy is used in order to validate our approach and to characterize the polarity of the material. Finally, simulations allow to quantify the impact of polar ETLs on device performance.

In standard unencapsulated poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methyl ester solar cells exposed to humid air, the oxidation of the aluminum cathode is known to be a key degradation mechanism. Water that enters the device at the edges and through pinholes diffuses to the organic–electrode interface. The forming oxide acts as a thin insulating layer that gives rise to an injection/extraction barrier and leads to a loss in the device current. In order to understand this behavior in detail various steady-state, transient, and impedance measurement techniques are performed in combination with drift-diffusion simulations. With this combinatorial approach the dominant degradation mechanism is confirmed to be the development of a blocking interface layer. This layer grows laterally leading to a loss in effective area due to the rapid local oxidation of the aluminum layer. Thus by combining multiple electrical techniques and optoelectrical simulations the dominant degradation mechanism can be evaluated. The same methodology is also beneficial for more stable and efficient novel solar cells.

Bilayer organic solar cells based on trimethine cyanine donor and C-60 acceptor materials have been fabricated by coating the trimethine dye from solution on molybdenum oxide (MoO3) anode buffer layer. The choice of deposition solvent drastically influences device performance, with 2,2,3,3-tetrafluoro-1-propanol (TFP) reducing the fill factor and power conversion efficiency of the device by 36 and 21%, respectively, as compared to chlorobenzene. In the case of TFP, extraction of photogenerated charge carriers by linearly increasing voltage (photo-CELIV) and capacitance- voltage analysis revealed the formation of a hole trapping zone at the molybdenum oxide interface which is also responsible for the S-shape current-voltage curve under white light irradiation. The transient charge extraction signal originating from trapped holes at the MoO3 interface could be clearly distinguished from the one relating to hole mobility in cyanine films using photo-CELIV measurements with varying delay times.

et al., The process of accurately gauging lifetime improvements in organic photovoltaics (OPVs) or other similar emerging technologies, such as perovskites solar cells is still a major challenge. The presented work is part of a larger effort of developing a worldwide database of lifetimes that can help establishing reference baselines of stability performance for OPVs and other emerging PV technologies, which can then be utilized for pass-fail testing standards and predicting tools. The study constitutes scanning of literature articles related to stability data of OPVs, reported until mid-2015 and collecting the reported data into a database. A generic lifetime marker is utilized for rating the stability of various reported devices. The collected data is combined with an earlier developed and reported database, which was based on articles reported until mid-2013. The extended database is utilized for establishing the baselines of lifetime for OPVs tested under different conditions. The work also provides the recent progress in stability of unencapsulated OPVs with different architectures, as well as presents the updated diagram of the reported record lifetimes of OPVs. The presented work is another step forward towards the development of pass-fail testing standards and lifetime prediction tools for emerging PV technologies., This work has been supported by the European Commission's StableNextSol COST Action MP1307. The research leading to these results has received funding from the European Union Seventh Framework Programme (FP7/2007-2013) under grant agreement n° 609788 (CHEETAH) and n° 290022 (ESTABLIS). ICN2 acknowledges the support of the Spanish MINECO through the Severo Ochoa Centers of Excellence Program under Grant Nos. SEV-2013-0295 and ENE2013-48816-C5-4-R. Thanks goes to Agencia de Gestio d'Ajuts Universitaris i de Recerca for the support through the Xarxa de Referencia en Materials Avançats per a l'Energia (XaRMAE) and consolidated research group No. 2014SGR-1212. This work has been carried out under the Materials Science Ph.D. Degree for A.M. of the Universitat Autònoma de Barcelona. R.R. and H.H. are grateful for financial support from BMBF (grant number 03EK3502) and ESF. F.P. received support from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement no. 659747. L.S. and M.R. received supported from the Portuguese Foundation for Science and Technology in the framework of the Strategic Program UID/FIS/04650/2013.

In this work we investigate polymer photodiodes based on a blend system consisting of poly(3-hexylthiophene-2,5-diyl) (P3HT) and the fullerene derivative (6,6)-phenyl C-butyric acid methyl ester (PCBM). An optimized low source impedance architecture allows measurements in the GHz range with minimum distortion, while at the same time allowing to probe the favourable sandwich device structure. We have studied the underlying device physics and investigated the influence of parameters such as active layer thickness and bias voltage on the transient photocurrent response. Using a numerical simulation software combining a self-consistent drift-diffusion model in conjunction with an optical model based on the transfer matrix method we model the transient photocurrent of polymer photodiodes. Transient photocurrent measurements utilizing this low impedance device architecture excited by 1.6 ns short laser pulses show very good correlation between simulated and measured results. Furthermore we have developed an encapsulation technique to integrate high-speed organic photodiodes onto standard printed circuit boards (PCBs) to avoid the degradation of the devices by humidity or oxygen.

Measured transient current voltage characteristics of organic solar cells exhibit a tail in the decline characteristic which is proportional to t−α. Common numerical drift-diffusion simulations neglecting dispersive charge carrier transport fail to describe the observed long tail of the current density decline up to micro seconds. Our approach is to account for the observed dispersive charge carrier transport by introducing an exponential distribution of trap states into our simulation. These trap states represent the tail of a bimodal distribution of energy states, which is commonly used to describe the distribution of transport sites of the highest occupied / lowest unoccupied molecular orbital (HOMO/LUMO) in organic materials. By doing so, we can reproduce the measured characteristics over four decades in time. Results are qualitatively and quantitatively in excellent accordance for different laser intensities, different applied biases and different device diameters at the same time.