This perspective summarizes how to accurately determine voltage losses and optical gaps, aiming to facilitate comparisons between organic photovoltaic materials.
Organic photodetectors have promising applications in low-cost imaging, health monitoring and near-infrared sensing. Recent research on organic photodetectors based on donor–acceptor systems has resulted in narrow-band, flexible and biocompatible devices, of which the best reach external photovoltaic quantum efficiencies approaching 100%. However, the high noise spectral density of these devices limits their specific detectivity to around 1013 Jones in the visible and several orders of magnitude lower in the near-infrared, severely reducing performance. Here, we show that the shot noise, proportional to the dark current, dominates the noise spectral density, demanding a comprehensive understanding of the dark current. We demonstrate that, in addition to the intrinsic saturation current generated via charge-transfer states, dark current contains a major contribution from trap-assisted generated charges and decreases systematically with decreasing concentration of traps. By modeling the dark current of several donor–acceptor systems, we reveal the interplay between traps and charge-transfer states as source of dark current and show that traps dominate the generation processes, thus being the main limiting factor of organic photodetectors detectivity.
High photon energy losses limit the open‐circuit voltage (VOC) and power conversion efficiency of organic solar cells (OSCs). In this work, an optimization route is presented which increases the VOC by reducing the interfacial area between donor (D) and acceptor (A). This optimization route concerns a cascade device architecture in which the introduction of discontinuous interlayers between alpha‐sexithiophene (α‐6T) (D) and chloroboron subnaphthalocyanine (SubNc) (A) increases the VOC of an α‐6T/SubNc/SubPc fullerene‐free cascade OSC from 0.98 V to 1.16 V. This increase of 0.18 V is attributed solely to the suppression of nonradiative recombination at the D–A interface. By accurately measuring the optical gap (Eopt) and the energy of the charge‐transfer state (ECT) of the studied OSC, a detailed analysis of the overall voltage losses is performed. Eopt – qVOC losses of 0.58 eV, which are among the lowest observed for OSCs, are obtained. Most importantly, for the VOC‐optimized devices, the low‐energy (700 nm) external quantum efficiency (EQE) peak remains high at 79%, despite a minimal driving force for charge separation of less than 10 meV. This work shows that low‐voltage losses can be combined with a high EQE in organic photovoltaic devices.
Organic solar cells usually utilise a heterojunction between electron-donating (D) and electron-accepting (A) materials to split excitons into charges. However, the use of D-A blends intrinsically limits the photovoltage and introduces morphological instability. Here, we demonstrate that polycrystalline films of chemically identical molecules offer a promising alternative and show that photoexcitation of α-sexithiophene (α-6T) films results in efficient charge generation. This leads to α-6T based homojunction organic solar cells with an external quantum efficiency reaching up to 44% and an open-circuit voltage of 1.61 V. Morphological, photoemission, and modelling studies show that boundaries between α-6T crystalline domains with different orientations generate an electrostatic landscape with an interfacial energy offset of 0.4 eV, which promotes the formation of hybridised exciton/charge-transfer states at the interface, dissociating efficiently into free charges. Our findings open new avenues for organic solar cell design where material energetics are tuned through molecular electrostatic engineering and mesoscale structural control.
Strong light-matter coupling can re-arrange the exciton energies in organic semiconductors. Here, we exploit strong coupling by embedding a fullerene-free organic solar cell (OSC) photo-active layer into an optical microcavity, leading to the formation of polariton peaks and a red-shift of the optical gap. At the same time, the open-circuit voltage of the device remains unaffected. This leads to reduced photon energy losses for the low-energy polaritons and a steepening of the absorption edge. While strong coupling reduces the optical gap, the energy of the charge-transfer state is not affected for large driving force donor-acceptor systems. Interestingly, this implies that strong coupling can be exploited in OSCs to reduce the driving force for electron transfer, without chemical or microstructural modifications of the photo-active layer. Our work demonstrates that the processes determining voltage losses in OSCs can now be tuned, and reduced to unprecedented values, simply by manipulating the device architecture.
Spectroscopic photodetection plays a key role in many emerging applications such as context‐aware optical sensing, wearable biometric monitoring, and biomedical imaging. Photodetectors based on organic semiconductors open many new possibilities in this field. However, ease of processing, tailorable optoelectronic properties, and sensitivity for faint light are still significant challenges. Here, the authors report a novel concept for a tunable spectral detector by combining an innovative transmission cavity structure with organic absorbers to yield narrowband organic photodetection in the wavelength range of 400–1100 nm, fabricated in a full‐vacuum process. Benefiting from this strategy, one of the best performed narrowband organic photodetectors is achieved with a finely wavelength‐selective photoresponse (full‐width‐at‐half‐maximum of ≈40 nm), ultrahigh specific detectivity above 1014 Jones, the maximum response speed of 555 kHz, and a large dynamic range up to 168 dB. Particularly, an array of transmission cavity organic photodetectors is monolithically integrated on a small substrate to showcase a miniaturized spectrometer application, and a true proof‐of‐concept transmission spectrum measurement is successfully demonstrated. The excellent performance, the simple device fabrication as well as the possibility of high integration of this new concept challenge state‐of‐the‐art low‐noise silicon photodetectors and will mature the spectroscopic photodetection into technological realities.
The low-energy edge of optical absorption spectra is critical for the performance of solar cells, but is not well understood in the case of organic solar cells (OSCs). We study the microscopic origin of exciton bands in molecular blends and investigate their role in OSCs. We simulate the temperature dependence of the excitonic density of states and low-energy absorption features, including low-frequency molecular vibrations and multi-exciton hybridisation. For model donor-acceptor blends featuring charge-transfer excitons, our simulations agree very well with temperature-dependent experimental absorption spectra. We unveil that the quantum effect of zero-point vibrations, mediated by electron-phonon interaction, causes a substantial exciton bandwidth and reduces the open-circuit voltage, which is predicted from electronic and vibronic molecular parameters. This effect is surprisingly strong at room temperature and can substantially limit the OSC's efficiency. Strategies to reduce these vibration-induced voltage losses are discussed for a larger set of systems and different heterojunction geometries.
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