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Multi-molecular excited states accompanied by an intra- and inter-molecular geometric relaxation are commonly encountered in optical and electrooptical studies and applications of organic semiconductors as, for example excimers or charge transfer states. Understanding the dynamics of these states is crucial to improve organic devices such as light emitting diodes and solar cells. Their full microscopic description, however, demands for sophisticated tools such as ab-initio quantum chemical calculations which come at the expenses of high computational costs and are prone to errors by assumptions as well as iterative algorithmic procedures. Hence, the analysis of spectroscopic data is often conducted on a phenomenological level only. Here, we present a toolkit to analyze temperature dependent luminescence data and gain first insights into the relevant microscopic parameters of the molecular system at hand. By means of a Franck-Condon based approach considering a single effective inter-molecular vibrational mode and different potentials for the ground and excited state we are able to explain the luminescence spectra of such multi-molecular states. We demonstrate that by applying certain reasonable simplifications the luminescence of charge transfer states as well as excimers can be satisfactorily reproduced for temperatures ranging from cryogenics to above room temperature. We present a semi-classical and a quantum-mechanical description of our model and, for both cases, demonstrate its applicability by analyzing the temperature depended luminescence of the amorphous donor-acceptor heterojunction tetraphenyldibenzoperiflanthene:C$_{60}$ as well as polycrystalline zinc-phthalocyanine to reproduce the luminescence spectra and extract relevant system parameters such as the excimer binding energy., Comment: manuscript: 16 pages, 6 figures; supplementary information: 12 pages, 7 figures

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.

By slowly evaporating organic solvents, we succeeded in growing lead-free double perovskite Cs2AgBiBr6 crystals. Solubility curves prove the advantage of this growth technique and allow comparison with the controlled cooling method. The growth temperature significantly affects the optical properties of the crystals, which enables us to better understand the material structure–property relationships.

Kinetic modelling has proven to be essential to understand the time and spatial dependence of charge carriers in solar cells. Traditional drift–diffusion simulations have generally been employed to describe static steady-state conditions, whereas recently the transient counterpart has been able to reveal more detailed information regarding carrier kinetics. In addition to customary electron and hole dynamics, perovskite materials are known to also be strongly affected by the displacement of lattice vacancies, charged atoms or even entire molecules. Such ionic motion transpires on vastly different time scales compared to free charges and are generally not straightforward to simultaneously account for in one transient simulation tool. Here, based on coding in Julia, we develop and use such a tool accounting for both the fast dynamics of free charges subjected to radiative, Shockley–Read–Hall and surface recombination, simultaneously as the very slow displacement of ions is properly accounted for. We show that interconnected steady-state parameters such as VOC and jSC as well as transient experimental voltage decay measurements can be accurately reproduced by our simulations. The vast time window, ranging from sub-microseconds to hours, provided by high-resolution open circuit voltage decay (OCVD) measurements combined with the steady-state parameters, is identified as a reliable gauge of artifact-free ionic dynamics in perovskite solar cells. With the knowledge gained from our simulations we can thus provide a straightforward experimental method providing direct access to values of ion concentration, and diffusivity as well as its thermal activation energy, parameters that are crucial for the future development and commercialization of perovskite-based photovoltaics.

Lead-free double perovskites have recently attracted growing attention as possible alternatives to lead-based halide perovskites in photovoltaics and other optoelectronic applications. The most pro...

The organic and hydrophobic polymer poly[N, N′-bis(4-butilphenyl)-N, N′-bis(phenyl)-benzidine] (polyTPD) represents a promising hole transport layer (HTL) for perovskite photovoltaics due to its suitable energy levels, whereby its highest occupied molecular orbital level matches well with the valence band level of methylammonium lead triiodide (CH3NH3PbI3, MAPbI3) perovskite. However, processing a perovskite layer from the solution on the surface of this organic material, is found to be difficult due to the surface properties of the latter. In this study, we evaluate efficient p-i-n type MAPbI3 perovskite solar cells employing differently processed polyTPD layers. We found that the surface coverage of the MAPbI3 perovskite layer strongly depends on the preparation method of the underlying polyTPD layer. By varying the solvents for the polyTPD precursor, its concentration, and by applying an optimised two-step perovskite deposition technique we increased both the surface coverage of the perovskite layer as well as the power conversion efficiency (PCE) of the corresponding solar cell devices. Our simple solvent-engineering approach demonstrates that no further interface modifications are needed for a successful preparation of efficient planar photovoltaic devices with PCEs in the range of 15 %–16 %.

The photovoltaic perovskite research community has now developed a large set of tools and techniques to improve the power conversion efficiency (PCE). One such arcane trick is to allow the finished devices to dwell in time, and the PCE often improves. Herein, a mild postannealing procedure is implemented on coevaporated perovskite solar cells confirming a substantial PCE improvement, mainly attributed to an increased open-circuit voltage (V\(_{OC}\)). From a V\(_{OC}\) of around 1.11 V directly after preparation, the voltage improves to more than 1.18 V by temporal and thermal annealing. To clarify the origin of this annealing effect, an in-depth device experimental and simulation characterization is conducted. A simultaneous reduction of the dark saturation current, the ideality factor (n\(_{id}\)), and the leakage current is revealed, signifying a substantial impact of the postannealing procedure on recombination losses. To investigate the carrier dynamics in more detail, a set of transient optoelectrical methods is first evaluated, ascertaining that the bulk carrier lifetime is increased with device annealing. Second, a drift-diffusion simulation is used, confirming that the beneficial effect of the annealing has its origin in effective bulk trap passivation that accordingly leads to a reduction of Shockley–Read–Hall recombination rates.

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 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

The lifetime of photogenerated charge carriers is one of the most important parameters in solar cells, as it rules the recombination rate that defines the open circuit voltage and the required minimum extraction time. It is therefore also one of the most discussed factors in all photovoltaic research fields. Lifetime evaluation of solar cells is frequently conducted via both optical and electrical means with the purpose of obtaining a deeper understanding of the dominant performance limiting recombination mechanisms. In many earlier recombination designations, performed via transient electrical means in novel thin film solar cells, the lifetime has been observed to be a decaying exponential function of the open circuit voltage. In this work we re-evaluate these previously assigned lifetimes as often being severely influenced by capacitive decay rates of spatially separated charge carriers. These “lifetimes” have thus very little in common with lifetimes relevant under steady state operational conditions of the solar cell. We show that the problem of lifetime determination via electrical means arises from that the relaxation of such charges, being associated with quasi-static capacitances of geometric type or from space-charge regions in the device, is also a decaying exponential function of the instantaneous open circuit voltage. This misconception hence also explains the often observed large discrepancy between optically and electrically determined lifetimes. We finally provide a simple expression outlining under what conditions relevant bulk recombination lifetimes are electrically accessible in thin film solar cells.

Transient photovoltage (TPV) is a technique frequently used to determine charge carrier lifetimes in thin-film solar cells such as organic, dye sensitized and perovskite solar cells. As this lifetime is often incident light intensity dependent, its relevance to understanding the intrinsic properties of a photoactive material system as a material or device figure of merit has been questioned. To extract complete information on recombination dynamics, the TPV measurements are often performed in conjunction with charge extraction (CE) measurements, employed to determine the photo-generated charge carrier density and thereby the recombination rate constant and its order. In this communication, the underlying theory of TPV and CE is reviewed and expanded. Our theoretical findings are further solidified by numerical simulations and experiments on organic solar cells. We identify regimes of the open-circuit voltage within which accurate lifetimes and carrier densities can be determined with TPV and CE experiments. A wide range of steady-state light intensities is required in performing these experiments in order to identify their 'working dynamic range' from which the recombination kinetics in thin-film solar cells can be determined.

One of the key properties of lead-halide perovskites employed in solar cells is the defect tolerance of the materials, in particular regarding intrinsic point defects, which mainly form shallow traps. Considering that high luminescence yields and photovoltaic performance are obtained by simple solution processing from commercial chemicals, it is commonly anticipated that the defect tolerance-at least to a considerable degree-extends to grain boundaries and extrinsic defects, i.e. impurities, as well. However, the effect of impurities has hardly been investigated. Here, we intentionally introduce small quantities of bismuth (10 ppm to 2%) in solution to be incorporated in the perovskite films based on mixed cation mixed anion compositions. We observe that Bi impurities in the %-regime reduce charge carrier collection efficiency and, more importantly, that the open-circuit voltage decreases systematically with impurity concentration even in the ppm regime. This strong defect intolerance against Bi impurities comes along with reduced electroluminescence yields and charge carrier lifetimes obtained from transient photoluminescence experiments. Calculations based on molecular dynamics and density functional theory predict delocalized (≈0.16 eV) and localized deep (≈0.51 eV) trap states dependent on the structural arrangement of the surrounding atoms. Structural characterization supports the idea of Bi being present as a homogeneously spread point defect, which substitutes the Pb2+ by Bi3+ as seen from XPS and a reduction of the lattice parameter in XRD. Sensitive measurements of the photocurrent (by FTPS) and surface photovoltage (SPV) confirm the presence of tail states. Photoelectron spectroscopy measurements show evidence of a deep state. These results are consistent with the common idea of shallow traps being responsible for the reduced charge collection efficiency and the decreased fill factor, and deeper traps causing a substantial reduction of the open-circuit voltage. As Bi is only one potential impurity in the precursor salts used in perovskite solar cell fabrication, our findings open-up a research direction focusing on identifying and eliminating impurities that act as recombination centers-a topic that has so far not been fully considered in device optimization studies. Fil: Yavari, M.. École Polytechnique Fédérale de Lausanne; Suiza Fil: Ebadi, Firouzeh. École Polytechnique Fédérale de Lausanne; Suiza Fil: Meloni, Simone. Università di Roma; Italia Fil: Wang, Zishuai. École Polytechnique Fédérale de Lausanne; Suiza Fil: Yang, Terry Chien-Jen. École Polytechnique Fédérale de Lausanne; Suiza Fil: Sun, Shijing. Massachusetts Institute Of Technology; Estados Unidos Fil: Schwartz, Heidi. University Of Cologne; Alemania Fil: Wang, Zaiwei. École Polytechnique Fédérale de Lausanne; Suiza Fil: Niesen, Bjoern. École Polytechnique Fédérale de Lausanne; Suiza Fil: Durantini, Javier Esteban. Universidad Nacional de Río Cuarto. Facultad de Ciencias Exactas Fisicoquímicas y Naturales. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados. - Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Tecnologías Energéticas y Materiales Avanzados; Argentina Fil: Rieder, Philipp. Julius Maximilian University Of Würzburg; Alemania Fil: Tvingstedt, Kristofer. Julius Maximilian University Of Würzburg; Alemania Fil: Buonassisi, Tonio. Massachusetts Institute Of Technology; Estados Unidos Fil: Choy, Wallace C.H.. The University Of Hong Kong; Hong Kong Fil: Filippetti, Alessio. Università Di Cagliari; Italia Fil: Dittrich, Thomas. Helmholtz Center Berlin For Materials And Energy; Alemania Fil: Olthof, Selina. University Of Cologne; Alemania Fil: Correa Baena, Juan Pablo. Massachusetts Institute Of Technology; Estados Unidos Fil: Tress, Wolfgang. École Polytechnique Fédérale de Lausanne; Suiza

Thin-film solar cells suffer from various types of recombination, of which leakage current usually dominates at lower voltages. Herein, we demonstrate first a three-order reduction of the shunt loss mechanism in planar methylammonium lead iodide perovskite solar cells by replacing the commonly used hole transport layer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with a better hole-selective polyarylamine. As a result, these cells exhibit superior operation under reduced light conditions, which we demonstrate for the extreme case of moonlight irradiance, at which open-circuit voltages of 530 mV can still be obtained. By the shunt removal we also observe the VOC to drop to zero after as long as 2 h after the light has been switched off. Second, at higher illumination intensities the dominant losses in the PEDOT:PSS-based cell are ascribed to surface recombination and are also proven to be substantially minimized by instead employing the polyarylamine. We attribute the reduced shunt and surface recombination to the far better suited semiconductor character of the polyarylamine, compared to that of PEDOT:PSS, efficiently blocking electrons from recombining at this electrode.

Guidelines for the correct measurement protocol of novel photovoltaic technologies such as perovskites are becoming more frequent in literature. This because, as will be confirmed in this perspective, it is not straightforward to correctly measure the efficiency parameters of these and many other novel solar cells. This is particularly the case for small area research devices which are prone to overestimate the short circuit current density, due to edge effects of various types. To reduce the inaccuracy of current density determination, the common recommended practice is to utilize masks with well‐defined apertures, often smaller than the device active area. Herein we show both experimentally and theoretically that this common practice however always leads to the erroneous determination of both open circuit voltage and fill factor, which are equally important figures of merit as the short circuit current density. Although the errors induced in voltage and fill factor by using a mask are generally smaller than what the errors in current can amount to when not using a mask, they are on the other hand omnipresent and can be quite well described.

Accurately identifying and understanding the dominant charge carrier recombination mechanism in perovskite solar cells are of crucial importance for further improvements of this already promising photovoltaic technology. Both optical and electrical transient methods have previously been employed to strive for this warranted goal. However, electrical techniques can be strongly influenced by the capacitive response of the device which hides the carrier recombination dynamics that are relevant under steady state conditions. To ascertain the identification of steady state relevant charge carrier dynamics, it is beneficial to evaluate thicker films to minimize the impact of device capacitance. Herein, the electrical transient response in very efficient planar co-evaporated n–i–p solar cells is studied by varying the active layer thickness from 500 nm to 820 nm and is compared to a solution-processed perovskite device with an active layer of 350 nm thickness. In the case of the n–i–p devices, the capacitance of the 500 nm solar cell leads to longer perceived decay times in the lower voltage regime, while in the higher voltage regime quite similar kinetics independent of the active layer thickness are observed, allowing us to identify the transition from capacitance-affected to the sought-after bulk charge carrier dynamics. We show that increasing the perovskite thickness by more than 50% does not affect the recombination dynamics significantly, confirming the high quality of the vacuum-processed perovskite solar cells. Finally, it is demonstrated for the first time for perovskite solar cells that the recombination order in both thicker devices ranges between 1.6 and 2, pointing towards trap-assisted and free-carrier recombination under operating conditions. We emphasize that the observed low recombination orders are in strong contrast to earlier literature as well as to the thinner solution-processed device, which suffers from both shorter carrier lifetimes and a larger device capacitance.

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').

The role of ions in organo-metal halide perovskites and its impact on optoelectronic device performance remains one of the most intriguing issues in the field. The current–voltage hysteresis often observed in hybrid perovskite solar cells has been assigned to the presence of mobile ions inside the perovskite layer. The difficulty in studying electronic properties of solar cells results from the screening effects as well as slow dynamics of mobile ions, particularly if they are located at the interfaces. In this work, we addressed the distribution of charged species in planar-type methylammonium lead iodine (MAPI) as well as formamidinium lead iodine (FAPI) solar cells by using a modified capacitance–voltage (CV) method without illumination in combination with a Mott–Schottky (MS) analysis of experimental data. The characteristic Mott–Schottky behavior with a linear dependence of C–2(V), distinctive for a pn-junction, is not visible in pristine devices. Surprisingly, biasing the device in the forward direc...

Adding cesium (Cs) and rubidium (Rb) cations to FA(0.83)MA(0.17)Pb(I0.83Br0.17)(3) hybrid lead halide perovskites results in a remarkable improvement in solar cell performance, but the origin of the enhancement has not been fully understood yet. In this work, time-of-flight, time-resolved microwave conductivity, and thermally stimulated current measurements are performed to elucidate the impact of the inorganic cation additives on the trap landscape and charge transport properties within perovskite solar cells. These complementary techniques allow for the assessment of both local features within the perovskite crystals and macroscopic properties of films and full devices. Strikingly, Csincorporation is shown to reduce the trap density and charge recombination rates in the perovskite layer. This is consistent with the significant improvements in the open-circuit voltage and fill factor of Cs-containing devices. By comparison, Rb-addition results in an increased charge carrier mobility, which is accompanied by a minor increase in device efficiency and reduced currentvoltage hysteresis. By mixing Cs and Rb in quadruple cation (Cs-Rb-FA-MA) perovskites, the advantages of both inorganic cations can be combined. This study provides valuable insights into the role of these additives in multiplecation perovskite solar cells, which are essential for the design of high-performance devices.

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.

Thin-film solar cells suffer from various types of recombination, of which leakage current usually dominates at lower voltages. Herein, we demonstrate first a three-order reduction of the shunt loss mechanism in planar methylammonium lead iodide perovskite solar cells by replacing the commonly used hole transport layer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with a better hole-selective polyarylamine. As a result, these cells exhibit superior operation under reduced light conditions, which we demonstrate for the extreme case of moonlight irradiance, at which open-circuit voltages of 530 mV can still be obtained. By the shunt removal we also observe the VOC to drop to zero after as long as 2 h after the light has been switched off. Second, at higher illumination intensities the dominant losses in the PEDOT:PSS-based cell are ascribed to surface recombination and are also proven to be substantially minimized by instead employing the polyarylamine. We attribute the reduced shunt and surface recombination to the far better suited semiconductor character of the polyarylamine, compared to that of PEDOT:PSS, efficiently blocking electrons from recombining at this electrode.

The charge carrier lifetime is an important parameter in solar cells as it defines, together with the mobility, the diffusion length of the charge carriers, thus directly determining the optimal active layer thickness of a device. Herein, we report on charge carrier lifetime values in bromine doped planar methylammonium lead iodide (MAPbI\(_3\)) solar cells determined by transient photovoltage. The corresponding charge carrier density has been derived from charge carrier extraction. We found increased lifetime values in solar cells incorporating bromine compared to pure MAPbI\(_3\) by a factor of ~2.75 at an illumination intensity corresponding to 1 sun. In the bromine containing solar cells we additionally observe an anomalously high value of extracted charge, which we deduce to originate from mobile ions.

In this work we present reflectance imaging as a suitable method for in situ monitoring of the drying process of film formation for organic photovoltaics (OPV) over large areas, as well as for lab- ...

The maximum efficiency of any solar cell can be evaluated in terms of its corresponding ability to emit light. We herein determine the important figure of merit of radiative efficiency for Methylammonium Lead Iodide perovskite solar cells and, to put in context, relate it to an organic photovoltaic (OPV) model device. We evaluate the reciprocity relation between electroluminescence and photovoltaic quantum efficiency and conclude that the emission from the perovskite devices is dominated by a sharp band-to-band transition that has a radiative efficiency much higher than that of an average OPV device. As a consequence, the perovskite have the benefit of retaining an open circuit voltage ~0.14 V closer to its radiative limit than the OPV cell. Additionally, and in contrast to OPVs, we show that the photoluminescence of the perovskite solar cell is substantially quenched under short circuit conditions in accordance with how an ideal photovoltaic cell should operate.

Semi-transparent (ST) organic solar cells with potential application as power generating windows are studied. The main challenge is to find proper transparent electrodes with desired electrical and optical properties. In this work, this is addressed by employing an amphiphilic conjugated polymer PFPA-1 modified ITO coated glass substrate as the ohmic electron-collecting cathode and PEDOT:PSS PH1000 as the hole-collecting anode. For active layers based on different donor polymers, considerably lower reflection and parasitic absorption are found in the ST solar cells as compared to solar cells in the standard geometry with an ITO/PEDOT:PSS anode and a LiF/Al cathode. The ST solar cells have remarkably high internal quantum efficiency at short circuit condition ( ∼ 90%) and high transmittance ( ∼ 50%). Hence, efficient ST tandem solar cells with enhanced power conversion efficiency ( PCE ) compared to a single ST solar cell can be constructed by connecting the stacked two ST subcells in parallel. The total loss of photons by reflection, parasitic absorption and transmission in the ST tandem solar cell can be smaller than the loss in a standard solar cell based on the same active materials. We demonstrate this by stacking fi ve separately prepared ST cells on top of each other, to obtain a higher photocurrent than in an optimized standard solar cell. Refereed/Peer-reviewed

In organic solar cells based on polymer:fullerene blends, energy is lost due to electron transfer from polymer to fullerene. Minimizing the difference between the energy of the polymer exciton (ED*) and the energy of the charge transfer state (ECT) will optimize the open-circuit voltage (Voc). In this work, this energy loss ED*-ECT is measured directly via Fourier-transform photocurrent spectroscopy and electroluminescence measurements. Polymer:fullerene photovoltaic devices comprising two different isoindigo containing polymers: P3TI and PTI-1, are studied. Even though the chemical structures and the optical gaps of P3TI and PTI-1 are similar (1.4 eV–1.5 eV), the optimized photovoltaic devices show large differences in Voc and internal quantum efficiency (IQE). For P3TI:PC71BM blends a ED*-ECT of ∼ 0.1 eV, a Voc of 0.7 V and an IQE of 87% are found. For PTI-1:PC61BM blends an absence of sub-gap charge transfer absorption and emission bands is found, indicating almost no energy loss in the electron transfer step. Hence a higher Voc of 0.92 V, but low IQE of 45% is obtained. Morphological studies and field dependent photoluminescence quenching indicate that the lower IQE for the PTI-1 system is not due to a too coarse morphology, but is related to interfacial energetics. Losses between ECT and qVoc due to radiative and non-radiative recombination are quantified for both material systems, indicating that for the PTI-1:PC61BM material system, Voc can only be increased by decreasing the non-radiative recombination pathways. This work demonstrates the possibility of obtaining modestly high IQE values for material systems with a small energy offset (

The field dependence of photocurrent found in many organic solar cells is a significant and detrimental setback for internal quantum efficiency. In this work we study the important contribution to this field dependence due to the dissociation efficiency of the weakly bound interfacial charge transfer (CT) state, crucial for organic bulk heterojunction solar cells. Three different donor polymers and two different acceptors are examined, and their respective dissociation characteristics are evaluated by photoluminescence (PL) quenching, both for Frenkel excitons and for the intermolecular charge transfer excitons. We observe that while the field-dependent photocurrent for pure polymers does correlate well with quenching efficiency, the CT exciton quenching from the blend generally displays a less pronounced correlation with extracted photocurrent. We further note that while the electroluminescence and photoluminescence of the pure polymer are identical, we observe a red shift for the blend electroluminescen...

The power conversion efficiency of polymer:fullerene bulk heterojunction solar cells depends on the generated photocurrent and photovoltage. Here we show, using the thermodynamic theory of detailed balance, that the photovoltage in particular is limited by the presence of polymer:fullerene material interaction, resulting in the formation of a weak donor-acceptor charge transfer complex (CTC). Excited CTCs, or charge transfer (CT) states, are visible in highly sensitive measurements of the absorption and photovoltaic action spectrum, or in photoluminescence and electroluminescence measurements. It is shown that photovoltaic and electroluminescent actions of the polymer: fullerene CTC are related by a reciprocity relation. This relation reproduces the measured open-circuit voltage (Voc) of the photovoltaic device under solar conditions. Also, the temperature and illumination intensity dependence of Voc is reproduced by the theory. Assuming perfect conditions for charge generation and recombination, a maximum obtainable Voc value in function of polymer:fullerene CTC properties is derived.

The synthesis of novel conjugated polymers, designed for the purpose of photovoltaic energy conversion, and their properties in polymer/fullerene materials and photovoltaic devices are reviewed. Two families of main-chain polymer donors, based on fluorene or phenylene and donor-acceptor-donor comonomers in alternating copolymers, are used to absorb the high-energy parts of the solar spectrum and to give high photovoltages in combinations with fullerene acceptors in devices. These materials are used in alternative photovoltaic device geometries with enhanced light incoupling to collect larger photocurrents or to enable tandem devices and enhance photovoltage. Refereed/Peer-reviewed

Efficient polymer solar cells typically contain the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), which promotes dissociation of excited states and enhances charge transpo ...

The increasing amount of research on solution-processable, organic donor-acceptor bulk heterojunction photovoltaic systems, based on blends of conjugated polymers and fullerenes has resulted in devices with an overall power-conversion efficiency of 6%. For the best devices, absorbed photon-to-electron quantum efficiencies approaching 100% have been shown. Besides the produced current, the overall efficiency depends critically on the generated photovoltage. Therefore, understanding and optimization of the open-circuit voltage (Voc) of organic solar cells is of high importance. Here, we demonstrate that charge-transfer absorption and emission are shown to be related to each other and Voc in accordance with the assumptions of the detailed balance and quasi-equilibrium theory. We underline the importance of the weak ground-state interaction between the polymer and the fullerene and we confirm that Voc is determined by the formation of these states. Our work further suggests alternative pathways to improve Voc of donor-acceptor devices.

In this article we report the weak but omnipresent electroluminescence (EL) from several types of organic polymer:fullerene bulk heterojunction solar cells biased in the forward direction. The light emitted from blends of some commonly used polymers and the fullerene molecule is significantly different from that of any of the pure materials comprising the blend. The lower energy of the blend EL is found to correlate with both the voltage onset of emission and the open-circuit voltage of the photovoltaic cell under solar illumination. We accordingly interpret the emission to originate from interfacial charge transfer state recombination and emphasize EL as a very valuable tool to characterize the charge transfer state present in donor/acceptor organic photovoltaic (OPV) cells.

Organic photovoltaic cells (OPV) are among the most promising systems for energy extraction and conversion from renewable energy sources. However, major problem to be solved before industrial production could become economically viable is represented by their still low conversion efficiency. The organic solar cell architectures are presently the result of a compromise between achieving complete light absorption using active layers that are thicker than the optical absorption length and achieving efficient charge collection at the electrodes which is favoured in thinner layers. We present a concept and its experimental demonstration that would solve efficiently the above trade-off problem by making use of a new type of light trapping elements. The simple fabrication scheme, based on a self-aligned UV exposure process, suggests its potential up-scalability to large systems, at low production cost.

Organic materials, such as conjugated polymers, have emerged as a promising alternative for the production of inexpensive and flexible photovoltaic cells. As conjugated polymers are soluble, liquid based printing techniques enable production on large scale to a price much lower than that for inorganic based solar cells. Present day state of the art conjugated polymer photovoltaic cells are comprised by blends of a semiconducting polymer and a soluble derivative of fullerene molecules. Such bulk heterojunction solar cells now show power conversion efficiencies of up to 4-6%. The quantum efficiency of thin film organic solar cells is however still limited by several processes, of which the most prominent limitations are the comparatively low mobility and the high level of charge recombination. Hence organic cells do not yet perform as well as their more expensive inorganic counterparts. In order to overcome this present drawback of conjugated polymer photovoltaics, efforts are continuously devoted to developing materials or devices with increased absorption or with better charge carrier transporting properties. The latter can be facilitated by increasing the mobility of the pure material or by introducing beneficial morphology to prevent carrier recombination. Minimizing the active layer film thickness is an alternative route to collect more of the generated free charge carriers. However, a minimum film thickness is always required for sufficient photon absorption. A further limitation for low cost large scale production has been the dependence on expensive transparent electrodes such as indium tin oxide. The development of cheaper electrodes compatible with fast processing is therefore of high importance. The primary aim of this work has been to increase the absorption in solar cells made from thin films of organic materials. Device construction, deploying new geometries, and evaluation of different methods to provide for light trapping and photon recycling have been strived for. Different routes to construct and incorporate light trapping structures that enable higher photon absorption in a thinner film are presented. By recycling the reflected photons and enhancing the optical path length within a thinner cell, the absorption rate, as well as the collection of more charge carriers, is provided for. Attempts have been performed by utilizing a range of different structures with feature sizes ranging from nanometers up to centimeters. Surface plasmons, Lambertian scatterers, micro lenses, tandem cells as well as larger folded cell structures have been evaluated. Naturally, some of these methods have turned out to be more successful than others. From this work it can nevertheless be concluded that proper light trapping, in thin films of organic materials for photovoltaic energy conversion, is a technique capable of improving the cell performance. In addition to the study of light trapping, two new alternative electrodes for polymer photovoltaic devices are suggested and evaluated.

Thermally stimulated current (TSC) measurements are used to characterize electronic trap states in methylammonium lead iodide perovsite solar cells. Several TSC peaks were observed over the temperature range from 20 K to room temperature. To elucidate the origins of these peaks, devices with various organic charge transport layers and devices without transport layers were tested. Two peaks appear at very low temperatures, indicating shallow trap states that are mainly attributed to the PCBM/C60 electron transport bilayer. However, two additional peaks appear at higher temperatures, that is, they are deeper in energy, and are assigned to the perovskite layer. At around T = 163 K, a sharp peak, also present in the dark TSC measurements, is assigned to the orthorhombic-tetragonal phase transition in the perovskite. However, a peak at around T = 191 K is assigned to trap states with activation energies of around 500 meV but with a rather low concentration of 1 × 10(21) m(-3).

A prototype solar cell with a transparent polymer cathode and an ITO/poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) anode was fabricated. As an active layer, a thin film of a bulk heterojunction of polyfluorene copolymer, poly[2,7-(9,9-dioctyl-fluorene)-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)] (APFO-3) and an electron acceptor mol. [6,6]-phenyl-C61-butyric acid Me ester (PCBM) (1:4 by wt.) was sandwiched between the 2 transparent polymer electrodes. The cathode is another form of PEDOT formed by vapor phase polymd. PEDOT (VPP PEDOT) with a cond. 102-103 S/cm. The cathode is supported on an elastomeric substrate and forms a conformal contact to the APFO-3/PCBM blend. Transparent solar cells are useful for building multilayer and tandem solar cells. [on SciFinder (R)]

Construction of luminescent single- and bilayer polymer arrays in micron and submicron scales through dewetting on a heterogeneous conducting polymer surface is demonstrated. We study the influence of the pattern geometry and film thickness of polymer dewetting upon annealing, and the morphology of created polymer arrays on the heterogeneous surface. The materials used for patterning are an insulating poly(methyl methacrylate) (PMMA) or a conjugated fluorescent polymer, poly(dioctylphenylthiophene) (PDOPT). The substrate used is the conducting polymer poly(3,4-ethylenedioxythiophene)–poly(styrenesulfonate) (PEDOT–PSS), with modified heterogeneous surface energy obtained by application of a bare polydimethylsiloxane (PDMS) stamp.

Triplet exciton formation in neat 7,7-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′] dithiophene-2,6-diyl)bis(6-fluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole) (p-DTS(FBTTh2)2) and blends with [6,6]-Phenyl C70 butyric acid methyl ester (PC70BM), with and without the selective solvent additive 1,8-diiodooctane, is investigated by means of spin sensitive photoluminescence measurements. For all three material systems, a significant amount of long living triplet excitons is detected, situated on the p-DTS(FBTTh2)2 molecules. The characteristic zero-field splitting parameters for this state are identified to be D = 42 mT (1177 MHz) and E = 5 mT (140 MHz). However, no triplet excitons located on PC70BM are detectable. Using electrically detected spin resonance, the presence of these triplet excitons is confirmed even at room temperature, highlighting that triplet excitons form during solar cell operation and influence the photocurrent and photovoltage. Surprisingly, the superior performing blend is found to have the largest triplet population. It is concluded, that the formation of triplet excitons from charge transfer states via electron back transfer has no crucial impact on device performance in p-DTS(FBTTh2)2:PC70BM based solar cells.

The value and temperature dependence of the ideality factor provides essential information about the dominant recombination route in solar cells. This study presents experimental results of accurate ideality factor determination for representative organic photovoltaic cells (OPV) evaluated at different temperatures over a large current density regime. It is noted that standard dark I–V curves strongly deviate from those obtained by evaluations based on short circuit current density (J SC)–open circuit voltage (V OC) pairs. This is attributed to the applied external voltage in a dark I–V measurement not being representative of internal chemical potential, particularly at lower temperatures. Complementary electroluminescence measurements attest that the current density dependence of the ability of the solar cell to emit light is better correlated to the series resistance free ideality factor. For the studied set of OPV devices it is observed that the ideality factors are quite low, and with very weak temperature dependence. The J SC–V OC method to determine ideality factors further allows good estimates of activation energies as well as recombination current prefactors J 00. The findings imply that the principal OPV non-radiative recombination mechanism is not recombination of free carriers with trapped carriers in an exponential density of tail states as previously reported.

An improved understanding of the electronic structure of interfacial charge transfer (CT) states is of importance due to their crucial role in charge carrier generation and recombination in organic donor-acceptor ($DA$) solar cells. $DA$ combinations with a small difference between the energy of the CT state (${E}_{\mathrm{CT}}$) and energy of the donor exciton (${E}_{{D}^{*}}$) are of special interest since energy losses due to electron transfer are minimized, resulting in an optimized open-circuit voltage. In that case, the CT state can be considered as a resonance mixture, containing character of a fully ionic state (${D}^{+}{A}^{\ensuremath{-}}$) and of the local polymer excited state (${D}^{*}A$). We show that the ${D}^{*}A$ contribution to the overall CT state wave function can be determined by measurements of the polarization anisotropy of CT absorption and emission of polymer:fullerene blends with aligned polymer chains. We study two donor polymers, P3HT and TQ1, blended with fullerene acceptors with different ionization potentials, allowing variation of the ${E}_{{D}^{*}}\ensuremath{-}{E}_{\mathrm{CT}}$ difference. We find that, upon decreasing ${E}_{{D}^{*}}\ensuremath{-}{E}_{\mathrm{CT}}$, the local excitonic ${D}^{*}A$ character of the CT state increases, resulting in a decreased fraction of charge transferred and an increased transition dipole moment. For typical polymer:fullerene systems, this effect is expected to become detrimental for device performance if ${E}_{{D}^{*}}\ensuremath{-}{E}_{\mathrm{CT}}l0.1$ eV. This however, depends on the electronic coupling between ${D}^{*}A$ and ${D}^{+}{A}^{\ensuremath{-}}$, which we experimentally estimate to be $\ensuremath{\sim}6$ meV for the TQ1:PCBM system.

Inverted polymer solar cells with a bottom metal cathode modified by a conjugated polymer interlayer show considerable improvement of photocurrent and fill factor, which is due to hole blocking at the interlayer, and a modified surface energy which affects the nanostructure in the TQ1/[70]PCBM blend. Refereed/Peer-reviewed

For an efficient conversion of photons to electrons by organic materials used for photovoltaic applications, the presence of a material interface between an electron-donating and electron-accepting material is crucial. This chapter deals with the interfacial charge transfer states formed at such interfaces under solar illumination. Absorption of long-wavelength light, with energy lower than the optical gap of both donor and acceptor results in the direct formation of these charge transfer states. Decay of CT states to the ground state will result in weak light emission. Both CT absorption and emission will be linked to photovoltaic performance. The role of the CT state in determining the open-circuit voltage is discussed in detail. We will also elaborate on the efficiency of dissociation and photocurrent generation from thermally relaxed CT states. Based on thermodynamical considerations and in the absence of nonradiative recombination, upper limits for the efficiency of organic solar cells based on donor–acceptor interfaces are derived and possible improvements and future research directions are indicated.

How 1,8-diiodooctane (DIO) enhances performance of polymer solar cells based on polymer HXS-1 and fullerene [6,6]-phenyl C(71)-butyric acid methyl ester (PC(71)BM) from 3.6% to 5.4% is scrutinized with several techniques by comparing devices or blend films spin-coated from dichlorobenzene (DCB) to those from DCB/DIO (97.5:2.5 v/v). Morphology of blend films is examined with atomic force microscopy (AFM), transmission electron microscopy (TEM) and electron tomography (3-D TEM), respectively. Charge generation and recombination is studied with photoluminescence, and charge transport with field effect transistors. The morphology with domain size in 10-20 nm and vertical elongated clusters formed in DIO system is supposed to facilitate charge transport and minimize charge carrier recombination, which are the main reasons for enhancing power conversion efficiency (PCE) from 3.6% (without DIO) to 5.4% (with DIO). Furthermore, a two year inspection shows no significant impact of DIO on the shelf-stability of the solar cells. No visible degradation in the second year indicates that the morphology of the active layers in the devices is relatively stable after initial relaxation in the first year. Original Publication: Weiwei Li, Yi Zhou, Viktor Andersson, Mattias Andersson, Yi Thomann, Clemens Veit, Kristofer Tvingstedt, Ruiping Qin, Zhishan Bo, Olle Inganäs, Uli Wuerfel and Fengling Zhang, The Effect of additive on performance and shelf-stability of HSX-1/PCBM photovoltaic devices, 2011, Organic electronics, (12), 9, 1544-1551. http://dx.doi.org/10.1016/j.orgel.2011.05.028 Copyright: Elsevier Science B.V., Amsterdam. http://www.elsevier.com/

Procedures for testing organic solar cell devices and modules with respect to stability and operational lifetime are described. The descriptions represent a consensus of the discussion and conclusions reached during the first 3 years of the international summit on OPV stability (ISOS). The procedures include directions for shelf life testing, outdoor testing, laboratory weathering testing and thermal cycling testing, as well as guidelines for reporting data. These procedures are not meant to be qualification tests, but rather generally agreed test conditions and practices to allow ready comparison between laboratories and to help improving the reliability of reported values. Failure mechanisms and detailed degradation mechanisms are not covered in this report. © 2011 Elsevier B.V. All rights reserved.

The open-circuit voltage (V-oc) of polymer:fullerene bulk heterojunction solar cells is determined by the interfacial charge-transfer (CT) states between polymer and fullerene. Fourier-transform photocurrent spectroscopy and electroluminescence spectra of several polymer:fullerene blends are used to extract the relevant interfacial molecular parameters. An analytical expression linking these properties to V-oc is deduced and shown to be valid for photovoltaic devices comprising three commonly used conjugated polymers blended with the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). V-oc is proportional to the energy of the CT states E-CT. The energetic loss q Delta V between E-CT and qV(oc) vanishes when approaching 0 K. It depends linearly on T and logarithmically on illumination intensity. Furthermore q Delta V can be reduced by decreasing the electronic coupling between polymer and fullerene or by reducing the nonradiative recombination rate. For the investigated devices we find a loss q Delta V of similar to 0.6 eV at room temperature and under solar illumination conditions, of which similar to 0.25 eV is due to radiative recombination via the CT state and similar to 0.35 eV is due to nonradiative recombination. Original Publication:Koen Vandewal, Kristofer Tvingstedt, Abay Gadisa, Olle Inganäs and Jean V Manca, Relating the open-circuit voltage to interface molecular properties of donor:acceptor bulk heterojunction solar cells, 2010, PHYSICAL REVIEW B, (81), 12, 125204.http://dx.doi.org/10.1103/PhysRevB.81.125204Copyright: American Physical Societyhttp://www.aps.org/