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Over the past decades, the field of organic solar cells (OSCs) has witnessed a significant evolution in materials chemistry, which has resulted in a remarkable enhancement of device performance, achieving efficiencies of over 19%. The photoactive layer materials in OSCs play a crucial role in light absorption, charge generation, transport and stability. To facilitate the scale-up of OSCs, it is imperative to address the photostability of these electron acceptor and donor materials, as their photochemical degradation process remains a challenge during the photo-to-electric conversion. In this review, we present an overview of the development of electron acceptor and donor materials, emphasizing the crucial aspects of their chemical stability behavior that are linked to the photostability of OSCs. Throughout each section, we highlight the photochemical degradation pathways for electron acceptor and donor materials, and their link to device degradation. We also discuss the existing interdisciplinary challenges and obstacles that impede the development of photostable materials. Finally, we offer insights into strategies aimed at enhancing photochemical stability and discuss future directions for developing photostable photo-active layers, facilitating the commercialization of OSCs. [ABSTRACT FROM AUTHOR]

Molecular doping plays an important role in controlling the carrier concentration of organic semiconductors. However, the introduction of dopant counterions often results in increased energetic disorder and traps due to the molecular packing disruption and Coulomb potential wells. To date, no general strategy has been proposed to reduce the counterion-induced structural and energetic disorder. Here, we demonstrate the critical role of non-covalent interactions (NCIs) between counterions and polymers. Employing a computer-aided approach, we identified the optimal counterions and discovered that NCIs determine their docking positions, which significantly affect the counterion-induced energetic disorder. With the optimal counterions, we successfully reduced the energetic disorder to levels even lower than that of the undoped polymer. As a result, we achieved a high n-doped electrical conductivity of over 200 S cm−1 and an eight-fold increase in the thermoelectric power factor. We found that the NCIs have substantial effects on doping efficiency, polymer backbone planarity, and Coulomb potential landscape. Our work not only provides a general strategy for identifying the most suitable counterions but also deepens our understanding of the counterion effects on doped polymeric semiconductors. Xiong et al. demonstrate the effects of non-covalent interactions between counterions and n-doped polymers on charge transport properties. They propose an approach, namely "counterion docking", for selecting optimal counterions in doping of organic semiconductors. [ABSTRACT FROM AUTHOR]

Poly(nickel-benzene-1,2,4,5-tetrakis(thiolate)) (Ni-btt), an organometallic coordination polymer (OMCP) characterized by the coordination between benzene-1,2,4,5-tetrakis(thiolate) (btt) and Ni2+ ions, has been recognized as a promising p-type thermoelectric material. In this study, we employed a constitutional isomer based on benzene-1,2,3,4-tetrakis(thiolate) (ibtt) to generate the corresponding isomeric polymer, poly(nickel-benzene-1,2,3,4-tetrakis(thiolate)) (Ni-ibtt). Comparative analysis of Ni-ibtt and Ni-btt reveals several common infrared (IR) and Raman features attributed to their similar square-planar nickel–sulfur (Ni–S) coordination. Nevertheless, these two polymer isomers exhibit substantially different backbone geometries. Ni-btt possesses a linear backbone, whereas Ni-ibtt exhibits a more undulating, zig-zag-like structure. Consequently, Ni-ibtt demonstrates slightly higher solubility and an increased bandgap in comparison to Ni-btt. The most noteworthy dissimilarity, however, manifests in their thermoelectric properties. While Ni-btt exhibits p-type behavior, Ni-ibtt demonstrates n-type carrier characteristics. This intriguing divergence prompted further investigation into the influence of OMCP backbone geometry on the electronic structure and, particularly, the thermoelectric properties of these materials. [ABSTRACT FROM AUTHOR]

Recent advances in light‐responsive materials enabled the development of devices that can wirelessly activate tissue with light. Here it is shown that solution‐processed organic heterojunctions can stimulate the activity of primary neurons at low intensities of light via photochemical reactions. The p‐type semiconducting polymer PDCBT and the n‐type semiconducting small molecule ITIC (a non‐fullerene acceptor) are coated on glass supports, forming a p–n junction with high photosensitivity. Patch clamp measurements show that low‐intensity white light is converted into a cue that triggers action potentials in primary cortical neurons. The study shows that neat organic semiconducting p–n bilayers can exchange photogenerated charges with oxygen and other chemical compounds in cell culture conditions. Through several controlled experimental conditions, photo‐capacitive, photo‐thermal, and direct hydrogen peroxide effects on neural function are excluded, with photochemical delivery being the possible mechanism. The profound advantages of low‐intensity photo‐chemical intervention with neuron electrophysiology pave the way for developing wireless light‐based therapy based on emerging organic semiconductors. [ABSTRACT FROM AUTHOR]

Molecular engineering of organic semiconductors provides a virtually unlimited number of possible structures, yet only a handful of combinations lead to state‐of‐the‐art efficiencies in photovoltaic applications. Thus, design rules that guide material development are needed. One such design principle is that in a bulk heterojunction consisting of an electron donor and lower bandgap acceptor an offset (ΔIE) of at least 0.45 eV is required between both materials ionization energies to overcome energy level bending at the donor–acceptor interface, in turn maximizing the charge separation yield and the cell's internal quantum efficiency. The present work studies energy losses associated with ΔIE and, based on 24 blends, finds that losses are minimal up to a ΔIE of 0.6 eV. Electroluminescence spectroscopy shows that low energy losses are achieved when the charge transfer state energy (ECT) is similar to the acceptor's optical bandgap (EgA). Further ΔIE increase lowers ECT with respect to EgA, thus decreasing VOC. Within that 0.45–0.6 eV ΔIE sweet range, the fill factor FF, hence the power conversion efficiency, increases only marginally as the FF is often already close to maximal for ΔIE = 0.45 eV. The results are extended to 76 binary and ternary blends. [ABSTRACT FROM AUTHOR]

Non‐fullerene acceptor (NFA)‐based ternary bulk heterojunction solar cells (TSC) are the most efficient organic solar cells (OSCs) today due to their broader absorption and quantum efficiencies (QE) often surpassing those of corresponding binary blends. The impact on QE of the energetics driving charge transfer at the electron donor:electron acceptor (D/A) interfaces is studied in blends of PBDB‐T‐2F donor with several pairs of lower bandgap NFAs. As in binary blends, the ionization energy offset between donor and acceptor (ΔIE) controls the QE and maximizes for ΔIE > 0.5 eV. However, ΔIE is not controlled by the individual NFAs IEs but by their average, weighted for their blending ratio. Using this property, the QE of a PBDB‐T‐2F:IEICO binary blend that has an insufficient ΔIE for charge generation is improved by adding a deep IE third component: IT‐4F. Combining two NFAs enables to optimize the D/A energy alignment and cells' QE without molecular engineering. [ABSTRACT FROM AUTHOR]

The organic photodiode (OPD) is a promising building block for solution‐processable, flexible, lightweight, and miniaturized photodetectors, ideal for wearable applications. Despite the advances in materials used in OPDs, their photocurrent and light responsivity are limited, and alternative methods are required to boost the signal response. Herein, a miniaturized organic electrochemical transistor (OECT) is integrated with an OPD module to unlock the potential of OPDs to acquire physiological signals. In this integrated photodetector (IPD) system, the light intensity regulates the OPD voltage output that modulates the OECT channel current. The high transconductance of the OECT provides efficient voltage‐to‐current conversion, enhancing the signal‐to‐noise ratio on the sensing site. A microscale, p‐type enhancement‐mode OECT with high gm and fast switching speed performs better in this application than depletion‐mode OECT of the same geometry. The IPD achieves a photocurrent and responsivity 318 and 140 times higher than the standalone OPD, respectively. It is shown that with the IPD, the amplitude of the photoplethysmogram signals detected by the OPD is enhanced by a factor of 2.9 × 103, highlighting its potential as a wearable biosensor and to detect weak, often uncaptured, light‐based signals from living systems. [ABSTRACT FROM AUTHOR]

Following the 2nd release of the "Emerging PV reports," the best achievements in the performance of emerging photovoltaic devices in diverse emerging photovoltaic research subjects are summarized, as reported in peer‐reviewed articles in academic journals since August 2021. Updated graphs, tables, and analyses are provided with several performance parameters, e.g., power conversion efficiency, open‐circuit voltage, short‐circuit current density, fill factor, light utilization efficiency, and stability test energy yield. These parameters are presented as a function of the photovoltaic bandgap energy and the average visible transmittance for each technology and application, and are put into perspective using, e.g., the detailed balance efficiency limit. The 3rd installment of the "Emerging PV reports" extends the scope toward triple junction solar cells. [ABSTRACT FROM AUTHOR]

The formation of photoinduced traps resulting in the loss of electron mobility deteriorates the performance of organic solar cells under continuous light soaking. The genesis of these loss mechanisms is elucidated by examining the structural stability of halogenated ITIC derivative films and the phase behavior of the respective binary systems by blending with the donor polymer PBDBT‐2F. Under constant illumination, ITIC‐4Cl is found to maintain its structural integrity, whereas fluorine on the peripheral moieties of ITIC‐4F undergoes chemical substitution to form a mixture of ITIC and ITIC‐4F. Thermal analysis of the light‐soaked binary films reveals that ITIC‐4Cl loses its crystalline phase while the crystallinity of ITIC‐4F does not undergo changes. Further, it is shown that the addition of a small amount of ITIC‐4F as a third component hinders the loss of ITIC‐4Cl crystalline phase in bulk heterojunction blends through the formation of cocrystals. These results suggest that long‐range ordering of NFAs does not necessarily improve the photostability of organic solar cells and that the addition of a third component, irrespective of the crystalline nature, can prevent changes in bulk heterojunction blend nanostructure. [ABSTRACT FROM AUTHOR]

The correct determination of the exciton diffusion length (LD) in novel organic photovoltaics (OPV) materials is an important, albeit challenging, task required to understand these systems. Herein, a high‐throughput approach to probe LD in nonfullerene acceptors (NFAs) is reported, that builds upon the conventional photoluminescence (PL) surface quenching method using NFA layers with a graded thickness variation in combination with spectroscopic PL mapping. The method is explored for two archetypal NFAs, namely, ITIC and IT‐4F, using PEDOT:PSS and the donor polymer PM6 as two distinct and practically relevant quencher materials. Interestingly, conventional analysis of quenching efficiency as a function of acceptor layer thickness results in a threefold difference in LD values depending on the specific quencher. This discrepancy can be reconciled by accounting for the differences in light in‐ and outcoupling efficiency for different multilayer architectures. In particular, it is shown that the analysis of glass/acceptor/PM6 structures results in a major overestimation of LD, whereas glass/acceptor/PEDOT:PSS structures give no significant contribution to outcoupling, yielding LD values of 6−12 and 8−18 nm for ITIC and IT‐4F, respectively. Hence, practical guidelines for quencher choice, sample geometries, and analysis approach for the accurate assessment of LD are provided. [ABSTRACT FROM AUTHOR]

Efficiencies of organic solar cells have practically doubled since the development of non‐fullerene acceptors (NFAs). However, generic chemical design rules for donor‐NFA combinations are still needed. Such rules are proposed by analyzing inhomogeneous electrostatic fields at the donor–acceptor interface. It is shown that an acceptor–donor–acceptor molecular architecture, and molecular alignment parallel to the interface, results in energy level bending that destabilizes the charge transfer state, thus promoting its dissociation into free charges. By analyzing a series of PCE10:NFA solar cells, with NFAs including Y6, IEICO, and ITIC, as well as their halogenated derivatives, it is suggested that the molecular quadrupole moment of ≈75 Debye Å balances the losses in the open circuit voltage and gains in charge generation efficiency. [ABSTRACT FROM AUTHOR]