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In the last decade, perovskite semiconductors have triggered a revolution in solar cell research. However, critical issues remain concerning the stability of metal-halide perovskites, which need to be overcome to enable a large scale commercialisation of perovskite photovoltaics (PV). While the rather poor environmental stability of these perovskites is usually attributed to their ionic nature rendering them sensitive to moisture and oxygen, the actual contribution of mobile ions to the total degradation loss under different environmental conditions is poorly understood. In this work, we reveal that the initial degradation of perovskite semiconductors is largely the result of mobile ion-induced internal field screening - a phenomenon that has not been previously discussed in relation to the degradation of perovskite solar cells. The increased field screening leads to a decrease in the steady-state power conversion efficiency mainly due to a large reduction in current density, while the efficiency at high scan speeds (>1000 V/s) where the ions are immobilized is much less affected. We also show that interfacial recombination does not increase upon ageing, yet the open-circuit voltage (VOC) decreases as the result of an increase in the mobile ion density upon ageing. Furthermore, similar ionic losses appear under different external stressors, in particular when there are free charges present in the absorber layer. This work reveals a key degradation mechanism, providing new insights into initial device degradation before chemical or extrinsic mechanical device degradation effects manifest, and it highlights the critical role mobile ions play therein.

In crystalline and amorphous semiconductors, the temperature-dependent Urbach energy can be determined from the inverse slope of the logarithm of the absorption spectrum and reflects the static and dynamic energetic disorder. Using recent advances in the sensitivity of photocurrent spectroscopy methods, we elucidate the temperature-dependent Urbach energy in lead halide perovskites containing different numbers of cation components. We find Urbach energies at room temperature to be 13.0 ± 1.0, 13.2 ± 1.0, and 13.5 ± 1.0 meV for single, double, and triple cation perovskite. Static, temperature-independent contributions to the Urbach energy are found to be as low as 5.1 ± 0.5, 4.7 ± 0.3, and 3.3 ± 0.9 meV for the same systems. Our results suggest that, at a low temperature, the dominant static disorder in perovskites is derived from zero-point phonon energy rather than structural disorder. This is unusual for solution-processed semiconductors but broadens the potential application of perovskites further to quantum electronics and devices.

The subtle link between photogenerated charge generation yield (CGY) and bimolecular recombination in organic semiconductor-based photovoltaics is relatively well established as a concept but has proven extremely challenging to demonstrate and probe especially under operational conditions. Received wisdom also teaches that charge generation in excitonic systems will always be lower than non-excitonic semiconductors such as GaAs – but this view is being challenged with the advent of organic semiconductor blends based upon non-fullerene acceptors (NFAs) with power conversion efficiencies exceeding 18%. Using a newly developed approach based upon temperature dependent ultra-sensitive external quantum efficiency measurements, we observe near unity CGY in several model NFA-based systems measured with unprecedented accuracy. We find that a relatively small increase in yield from 0.984 to 0.993 leads to a reduction in bimolecular recombination from 400 times to 1000 times relative to the Langevin limit. In turn, this dramatic reduction delivers the best thick junction performance to date in any binary organic solar cell – notably 16.2% at 300 nm. The combination of high efficiency and thick junction is the key for industrial fabrication of these devices via high-throughput deposition processing such as roll-to-roll, and thus central to a viable solar cell technology. These results also clearly reveal and elucidate the relationship between photo-generation and recombination in excitonic semiconductor photovoltaics thus providing an important bridge between basic device physics and practical cell engineering.

Inherently narrowband near-infrared organic photodetectors are highly desired for many applications, including biological imaging and surveillance. However, they suffer from a low photon-to-charge conversion efficiencies and utilize spectral narrowing techniques which strongly rely on the used material or on a nano-photonic device architecture. Here, we demonstrate a general and facile approach towards wavelength-selective near-infrared phtotodetection through intentionally n-doping 500-600 nm-thick nonfullerene blends. We show that an electron-donating amine-interlayer can induce n-doping, resulting in a localized electric field near the anode and selective collection of photo-generated carriers in this region. As only weakly absorbed photons reach this region, the devices have a narrowband response at wavelengths close to the absorption onset of the blends with a high spectral rejection ratio. These spectrally selective photodetectors exhibit zero-bias external quantum efficiencies of similar to 20-30% at wavelengths of 900-1100 nm, with a full-width-at-half-maximum of 10(12) Jones. The authors thank Guy. Brammertz at IMEC for capacitance measurements. We also thank the Research Foundation Flanders (FWO Vlaanderen) for continuing financial support (projects G0D0118N, G0B2718N, 1S50820N, 11D2618N), as well as the European Research Council (ERC, grant agreement 864625). Q.L. acknowledges financial support from the European Union’s Horizon 2020 research and innovation program under the Marie-Curie grant agreement no. 882794. S.G. acknowledges the FWO for his Ph.D fellowship. H.-G.B. and D.D. are very grateful to FWO for funding the HAXPES-lab instrument within the HERCULES program for large research infrastructure of the Flemish government. A.A. acknowledges support from Sêr Cymru II Program through the European Regional Development Fund and the Welsh European Funding Office.

Funder: Alexander von Humboldt Foundation; Id: http://dx.doi.org/10.13039/100005156, Perovskite semiconductors are an attractive option to overcome the limitations of established silicon based photovoltaic (PV) technologies due to their exceptional opto‐electronic properties and their successful integration into multijunction cells. However, the performance of single‐ and multijunction cells is largely limited by significant nonradiative recombination at the perovskite/organic electron transport layer junctions. In this work, the cause of interfacial recombination at the perovskite/C60 interface is revealed via a combination of photoluminescence, photoelectron spectroscopy, and first‐principle numerical simulations. It is found that the most significant contribution to the total C60‐induced recombination loss occurs within the first monolayer of C60, rather than in the bulk of C60 or at the perovskite surface. The experiments show that the C60 molecules act as deep trap states when in direct contact with the perovskite. It is further demonstrated that by reducing the surface coverage of C60, the radiative efficiency of the bare perovskite layer can be retained. The findings of this work pave the way toward overcoming one of the most critical remaining performance losses in perovskite solar cells.

The photogeneration of free charges in light-harvesting devices is a multistep process, which can be challenging to probe due to the complexity of contributing energetic states and the competitive character of different driving mechanisms. In this contribution, we advance a technique, integral-mode transient charge extraction (ITCE), to probe these processes in thin-film solar cells. ITCE combines capacitance measurements with the integral-mode time-of-flight method in the low intensity regime of sandwich-type thin-film devices and allows for the sensitive determination of photogenerated charge-carrier densities. We verify the theoretical framework of our method by drift-diffusion simulations and demonstrate the applicability of ITCE to organic and perovskite semiconductor-based thin-film solar cells. Furthermore, we examine the field dependence of charge generation efficiency and find our ITCE results to be in excellent agreement with those obtained via time-delayed collection field measurements conducted on the same devices.

Photodiodes are ubiquitous in industry and consumer electronics. New applications for photodiodes are constantly emerging, such as the internet of things and wearable electronics that demand different mechanical and optoelectronic properties from those provided by conventional inorganic devices. This has stimulated considerable interest in the use of next generation semiconductors, particularly the organics, which provide a vast palette of available optoelectronic properties, can be incorporated into flexible form factor geometries, and promise extremely low cost, low embodied energy manufacturing from earth abundant materials. The sensitivity of a photodiode to low light intensities (typically important in these new applications) depends critically on the dark current. Organic photodiodes, however, are characterized by a much higher dark current than expected for thermally excited band-to-band transitions. Here, we show that the lower limit of the dark current is given by recombination via mid-gap trap states. This new insight is generated from temperature dependent dark current measurements of narrow-gap photodiodes for the near-infrared. Based on Shockley-Read-Hall statistics, a diode equation is derived which can be used to determine an upper limit for the specific detectivity and to explain the general trend observed for the light to dark current ratio as a function of the experimental open-circuit voltage for a series of organic photodiodes. A detailed understanding of the origins of noise in any detector is fundamental to defining performance limitations and thus is critical to materials and device selection, design and optimisation for all applications. Our work establishes these important principles for organic semiconductor photodiodes for the near-infrared.

The spectral shape near the energy gap determines the radiative limit of the open-circuit voltage in organic photovoltaic devices. In this work, we employ ultrasensitive photocurrent measurements and detect sub-gap states with energies far below gap in a large number of different donor-acceptor blends. We provide evidence that these low-energy sub-gap states are associated with radiative mid-gap trap states, generating photocurrent via an optical release process. To account for the radiative mid-gap states, we implement a two-diode model which accurately describes both the dark current and the open-circuit voltage in organic solar cells. These findings provide important insights for our current understanding of organic photovoltaic devices.

Non-radiative losses to the open-circuit voltage are a primary factor in limiting the power conversion efficiency of organic photovoltaic solar cells. The dominate non-radiative loss is intrinsic to the active layer which, along with the thermodynamic limit to the open-circuit voltage, define the quasi-Fermi level splitting (QFLS). Quantification of the QFLS in organic photovoltaic devices is challenging due to the excitonic nature of photoexcitation and device-related non-radiative losses. In this presentation I will outline an experimental approach based on electro-modulated photoluminescence to quantify the QFLS in organic solar cells. Drift-diffusion simulations are used to verify the accuracy of the method, while state-of-the art PM6:Y6 solar cells are created with varying non-radiative losses. This method quantifies the QFLS in organic photovoltaics, fully characterizing the magnitude of different contributions to the non-radiative losses of the open-circuit voltage.

Recent advances in organic solar cell material development based around non-fullerene electron acceptors in bulk heterojunctions have propelled power conversion efficiencies to >18%, with 20% on the horizon and 25% predicted. These efficiencies are close to traditional inorganic semiconductor photovoltaics and thus focus is now turning to manufacturability and creating a viable solar cell technology. In this presentation we report the highest efficiency to date (16% with a Fill Factor >70%) in a thick junction binary organic solar cell based upon PM6:BTP-eC9. Using a very accurate approach based upon temperature dependent ultra-sensitive EQE measurements we find that this system (and a similar one based upon PM6:Y6) have near unity charge generation yields (CGY > 99%). In this regime, we observe that a small increase in CGY of only 0.5% leads to a 2.5 times more reduction in bimolecular recombination relative to the Langevin limit enabling high efficiency thick junction solar cells.

Probing the photovoltaic external quantum efficiency (EQE) at photon energies well below the semiconductor bandgap is an important tool for achieving a better understanding of the contribution of trap and tail states involved in charge generation processes in photovoltaic devices, notably solar cells. In this work, we present an electrical and optical noise-reduced EQE apparatus achieving 100 dB dynamic range. We carefully identify and study several device- and EQE apparatus-related factors limiting the EQE measurement sensitivity. Minimizing these factors allows us to detect photocurrents smaller than a fA, corresponding to EQE signals as small as -100 dB. We use these ultra-sensitive EQE measurements to probe weak sub-bandgap absorption features in organic, inorganic and perovskite semiconductors. In this regard, we directly observe photocurrent-contributing sub-gab trap states in organic solar cells significantly lower in energy than the corresponding charge-transfer state.

Trap-assisted recombination caused by localised sub-gap states is one of the most important first-order loss mechanism limiting the power-conversion efficiency of all solar cells. The presence and relevance of trap-assisted recombination in organic photovoltaic devices is still a matter of some considerable ambiguity and debate, hindering the field as it seeks to deliver ever higher efficiencies and ultimately a viable new solar photovoltaic technology. In this work, we show that trap-assisted recombination loss of photocurrent is universally present under operational conditions in a wide variety of organic solar cell materials including the new non-fullerene electron acceptor systems currently breaking all efficiency records. The trap-assisted recombination is found to be induced by states lying 0.35-0.6 eV below the transport edge, acting as deep trap states at light intensities equivalent to 1 sun. Apart from limiting the photocurrent, we show that the associated trap-assisted recombination via these comparatively deep traps is also responsible for ideality factors between 1 and 2, shedding further light on another open and important question as to the fundamental working principles of organic solar cells. Our results also provide insights for avoiding trap-induced losses in related indoor photovoltaic and photodetector applications., Trap-assisted recombination caused by localised sub-gap states is one of the factors limiting power-conversion efficiency in solar cells, yet the presence and relevance is still under debate in organic solar cells. Here, the authors reveal that this recombination loss is universally present under operational conditions in these devices.

Non-fullerene acceptors (NFAs) are far more emissive than their fullerene-based counterparts. Here, we study the spectral properties of photocurrent generation and recombination of the blend of the...

The impact of intermixed donor-acceptor domains in organic bulk heterojunction (BHJ) solar cells, using low-donor-content devices as model systems, is clarified. At low donor contents, the devices are found to exhibit anomalously high open-circuit voltages independent of the donor-acceptor energetics. These observations can be consistently explained by a theoretical model based on optical release of trapped holes, assuming the donors behave as trap sites in the gap of the acceptor. Our findings provide guidelines for reducing the large open-circuit voltage losses in organic solar cells and avoiding morphology-induced losses in state-of-the-art BHJ solar cells and photodetectors.

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").