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[Display omitted] • A pair of novel metal-free chiral molecular ferroelectric semiconductors was prepared. • Construction of narrow band gap structures by introducing polyiodide anions. • Designing ferroelectrics with helical arrangement by chiral chemical means. • The initial application in photovoltaics is demonstrated. Ferroelectric semiconductors have gained significant attraction for designing photovoltaic devices. However, their wide bandgap results in poor absorption of visible light. Herein, we report a pair of chiral metal-free molecular ferroelectric semiconductors (1 R ,4 R /1 S ,4 S - C 5 H 10 NO)I 3 (R/S-OABHI ; (1 R ,4 R /1 S ,4 S - C 5 H 10 NO)+ = 1 R ,4 R /1 S ,4 S -2-oxa-5-azabicyclo[2.2.1]heptonium) with notable ferroelectricity (saturation polarization of ∼6.8 and 6.1 μC/cm2 for R-/S-OABHI , respectively). They demonstrate an appropriate photovoltaic bandgap of ∼ 1.41 and 1.39 eV for R-/S-OABHI , respectively, comparable to MAPbI 3 (MA = methylammonium). Experiments and computational simulations reveal that the ferroelectricity of R / S-OABHI originates from their non-centrosymmetric crystal packing in a controllable helical manner, while the I 3 − contributes to band edges. Meanwhile, photovoltaic effect is firstly observed in the R-OABHI based solar cell with an open-circuit voltage of 0.581 V and a short-circuit current density of 1.734 mA/cm2. Overall, we establish a new approach for realizing metal-free ferroelectric photovoltaics, and it will pave the way for the exploration of multifunctional chiral molecular ferroelectrics. [ABSTRACT FROM AUTHOR]

• Acceptor fluorination leads to increased voltage losses in organic solar cells. • The increased voltage loss is associated with increased reorganization energy. • A side chain modification strategy is proposed to address the voltage loss issue. Acceptor fluorination is a commonly employed molecular modification strategy aimed at enhancing the quantum efficiency and charge carrier transport properties of organic solar cells. However, this approach often leads to a significant reduction in the open-circuit voltage (V oc) of the solar cells, thereby limiting their overall performance. In this study, we investigate the limitation of V oc in organic solar cells based on fluorinated acceptors. Our investigation reveals that the reduced V oc can be attributed to increased voltage losses (V loss), primarily arising from more significant non-radiative voltage losses originating from a decline in the external quantum efficiency of electroluminescence (EQE EL). Furthermore, we establish that the reduced EQE EL is a result of deteriorated molecular packing, which leads to an elevated reorganization energy. To address the high V loss and limited performance observed in solar cells utilizing fluorinated acceptors, we propose a strategy involving acceptor side-chain modifications. These results provide new insights into enhancing the performance of organic solar cells. [ABSTRACT FROM AUTHOR]

• Increasing donor side chain size leads to reduced CT dissociation efficiency. • Increasing acceptor side chain size results in reduced device voltage losses. • Highest PCE is realized when both the donor and acceptor are with large side chains. Increasing the size of the side chains of the donor or the acceptor materials is a highly effective strategy to reduce voltage losses, and increase the open-circuit voltage (Voc) of organic solar cells (OSCs). However, higher Voc does not necessarily translate to improved overall performance. To optimize side-chains and improve the performance of OSCs, the origin of the impact of the increased size of the donor and/or acceptor side side-chains size on the performance of OSCs is investigated. The study demonstrates that increasing the size of donor side chains can increase Voc, but it can also lead to deteriorated molecular packing, limiting overall solar cell performance. On the other hand, increasing the size of acceptor side chains can also increase Voc and improve molecular packing properties of the active layer, resulting in improved solar cell performance. Finally, the study shows that the best photovoltaic performance is achieved when both the donor and acceptor have large side chains. This research establishes the relationship between side chains of active materials, molecular packing properties, and the energetics of the donor/acceptor active layer, which is crucial for overcoming performance bottlenecks in OSCs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Three small molecular acceptors were designed and synthesized. • Noncovalent Conformational Locks and Side-Chain Engineering can adjust the properties of acceptors. • Significantly different power conversion efficiencies of 12.09%, 12.30% and 14.25% are achieved. Three novel small molecular acceptors (SMAs) BO-2F , BO-C8-2F and BO-C2C6-C8-2F were designed and synthesized. These acceptors all possess planar molecular backbone because of the introduction of intramolecular noncovalent interaction. Among them, BO-C2C6-C8-2F with four side chains, which has the highest solubility, can form more appropriate nanomorphology when blending with PBDB-T. Hence, organic solar cells (OSCs) based on PBDB-T: BO-C2C6-C8-2F displayed an outstanding power convesion efficiency (PCE) of 14.25%, which is higher than BO-2F and BO-C8-2F based ones. To the best of our knowledge, the PCE of 14.25% is one of the highest for the OSCs based on A-π-D-π-A type SMAs. Our results have demonstrated that the combination of side-chain engineering and intramolecular conformation lock has a great prospect in the design of high performance SMAs for OSCs. [ABSTRACT FROM AUTHOR]

• Minor terminal and central changes endow DO-2F and FO-N complementary absorption. • Asymmetrical FO-N effectively suppress the self-aggregation of DO-2F. • Acceptor alloy is found between the FO-N and DO-2F. • Alloy state acceptors produce suitable morphology with reduced V nr of 0.23 eV. • FO-N is an excellent third component for highly efficient OSCs of 14.10% Nonfused ring acceptors have shown great potential for future commercial applications of organic solar cells (OSCs) due to their simple structure and low synthetic costs. Herein, a novel asymmetrical nonfused ring acceptor FO-N with one branched lateral chain and one fluoro substituent at the central phenylene core was designed and introduced into PBDB-T : DO-2F binary system to fabricate high-efficiency ternary OSCs. The high-lying LUMO level of FO-N is conducive to improve V oc for ternary devices. More importantly, the introduction of FO-N as the third component can efficiently improve the compatibility of the ternary system via tuning the crystal size and optimizing the blend film morphology, which is beneficial to charge separation and reduced the non-radiative energy loss (Δ E nonrad). Finally, the ternary device achieved a low Δ E nonrad of 0.23 eV and a greatly improved PCE of 14.10% and with a V oc of 0.88 V, a J sc of 21.48 mA/cm2 and an FF of 74.41%. These results imply that the asymmetric nonfused ring acceptor design strategy is an effective way for optimizing the photovoltaic performance of highly crystallized blend system. [ABSTRACT FROM AUTHOR]