Recent efforts in organic photovoltaics (OPVs) have been devoted to obtaining low-bandgap non-fullerene acceptors (NFAs) for high photocurrent generation. However, the low-lying lowest unoccupied molecular orbital (LUMO) level in narrow bandgap NFAs typically results in a small energy difference (ΔEDA) between the LUMO of the acceptor and the highest occupied molecular orbital (HOMO) of the donor, leading to low open-circuit voltage (VOC). The trade-off between ΔEDA and photocurrent generation significantly limits the simultaneous enhancement of both VOC and short-circuit current density (JSC). Here, we report a new medium-bandgap NFA, IDTT-T, containing a weakly electron-withdrawing N-ethyl thiabarbituric acid terminal group on each end of the indacenodithienothiophene (IDTT) core. When paired with a benchmark low-bandgap PTB7-th polymer donor, simultaneous enhancement of both ΔEDA and absorption spectral coverage was realized. The OPV devices yield a VOC of 1.01 V, corresponding to a low energy loss of 0.57 eV in around 10% efficiency single-junction NFA OPVs. The design demonstrates a working principle to concurrently increase ΔEDA and photocurrent generation for high VOC and PCE in bulk fullerene-free heterojunction OPVs.

High boiling-point solvent additives, such as 1,8-diiodooctane, have been widely used to tune nanoscale phase morphology for increased efficiency in bulk heterojunction organic solar cells. However, liquid-state solvent additives remain in the active films for extended times and later migrate or evaporate from the films, leading to unstable device performance. Here, a solid-state photoactive molecular mediator, namely N(BAI)3, is reported that could be employed to replace the commonly used solvent additives to tune the morphology of bulk heterojunction films for improved device performance. The N(BAI)3 mediator not only resides in the active films locally to fine tune the phase morphology, but also contributes to the additional absorption of the active films, leading to ∼11% enhancement of power conversion efficiency of P3HT:PC60BM devices. Comparative studies are carried out to probe the nanoscale morphologies using grazing incidence wide-angle X-ray scattering and complementary neutron reflectometry. The use of 1 wt% N(BAI)3 is found to effectively tune the packing of P3HT, presumably through balanced π-interactions endowed by its large conjugated π surface, and to promote the formation of a PC60BM-rich top interfacial layer. These findings open up a new way to effectively tailor the phase morphology by photoactive molecular mediators in organic photovoltaics.

The introduction of B ← N coordinate bond-isoelectronic to C-C single bond-into π-systems represents a promising strategy to impart exotic redox and electrochromic properties into conjugated organic molecules and macromolecules. To achieve both reductive and oxidative activities using this strategy, a cruciform ladder-type molecular constitution was designed to accommodate oxidation-active, reduction-active, and B ← N coordination units into a compact structure. Two such compounds (BN-F and BN-Ph) were synthesized via highly efficient N-directed borylation. These molecules demonstrated well-separated, two reductive and two oxidative electron-transfer processes, corresponding to five distinct yet stable oxidation states, including a rarely observed boron-containing radical cation. Spectroelectrochemical measurements revealed unique optical characteristics for each of these reduced/oxidized species, demonstrating multicolor electrochromism with excellent recyclability. Distinct color changes were observed between each redox state with clear isosbestic points on the absorption spectra. The underlying redox mechanism was elucidated by a combination of computational and experimental investigations. Single-crystal X-ray diffraction analysis on the neutral state, the oxidized radical cation, and the reduced dianion of BN-Ph revealed structural transformations into two distinct quinonoid constitutions during the oxidation and reduction processes, respectively. B ← N coordination played an important role in rendering the robust and reversible multistage redox properties, by extending the charge and spin delocalization, by modulating the π-electron density, and by a newly established hyperconjugation mechanism.

Three series of low-bandgap polymers based on a novel quinoidal para-azaquinodimethane (p-AQM) unit are devised and synthesized, enabling an in-depth study of the impact of structural factors such as polymer main chain, branching point of the side chain, and the length of the branch chains on the thin film morphologies and charge transport properties. Morphological studies reveal that the polymers composed of larger repeating units exhibit a stronger tendency to form edge-on lamella. On the other hand, altering the side chain structures of polymers with the same main chain configuration indicates that the branching point position has a more deterministic impact than the branch chain length on the interchain interactions and the crystallite orientation. These results demonstrate a compound odd-even effect of the branching point on the chain packing and morphology, which correlates well with the corresponding field effect transistor performances. The polymer with the branching point at the fourth carbon displays the highest charge carrier mobility over 1.0 cm2 V−1 s−1, concurrent with a bimodal texture. This study provides a comprehensive description of the correlations between polymer structures, thin film morphology, and device performances, providing a clear path to desirable bimodal thin film texture for charge transport.

Herein, high-performance printed all-polymer solar cells (all-PSCs) based on a bulk-heterojunction (BHJ) blend film are demonstrated using PTzBI as the donor and N2200 as the acceptor. A slot-die process is used to prepare the BHJ blend, which is a cost-effective, high-throughput approach to achieve large-area photovoltaic devices. The real-time crystallization of polymers in the film drying process is investigated by in situ grazing incidence wide-angle X-ray scattering characterization. Printing is found to significantly improve the crystallinity of the polymer blend in comparison with spin coating. Moreover, printing with 1,8-diiodooctane as the solvent additive enhances the polymer aggregation and crystallization during solvent evaporation, eventually leading to multi-length-scale phase separation, with PTzBI-rich domains in-between the N2200 crystalline fibers. This unique morphology achieved by printing fabrication results in an impressively high power conversion efficiency of 9.10%, which is the highest efficiency reported for printed all-PSCs. These findings provide important guidelines for controlling film drying dynamics for processing all-PSCs.

Black phosphorus (BP) as a promising two-dimensional (2D) material has gained great attention in nanoelectronic devices because of its intrinsic semiconductor characteristics. However, the poor material availability and solution processability have been major roadblocks that hinder its wider application in microelectronics. Herein, readily available, lost-cost BP was utilized as an effective component that was integrated via a facile solution process for the fabrication of bulk heterojunction organic solar cells (OSCs). An impressive fill factor (FF) of 74.2% and power conversion efficiency (PCE) of 10.5% were realized in the OSCs incorporating 10 wt% of BP in the active layer of the benchmark polymer donor PTB7-Th and PC71BM acceptor, corresponding to a 20% PCE enhancement compared to the BP-free binary devices. The efficiency enhancement can be attributed to BP's high hole carrier mobility that facilitates better carrier extraction and suppression of the recombination. BP has been further demonstrated to be effective in additional solar cells based on other photovoltaic (PV) materials, including non-fullerene OSCs. The successful incorporation of the inexpensive BP in the solution-based fabrication of OSCs opens the door for its application in high performance, low cost flexible electronics.

Ternary structure is an important design strategy to obtain high-efficiency non-fullerene organic photovoltaics (OPVs). However, the role of the third component to the standard binary system is still unclear. Here, a wide-bandgap small-molecule acceptor, denoted IDT-T, is synthesized and used together with a wide-bandgap donor polymer, PBDB-T, and a low-bandgap acceptor, ITIC, for fullerene-free ternary solar cells. The ternary cell features an enhanced power conversion efficiency (PCE) up to 12.2%, together with improved photocurrent density, open-circuit voltage (VOC), and fill factor. Studies of the thin films indicate that IDT-T functions as an energy-level mediator, a fluorescence resonance energy-transfer donor, an electron acceptor, and a crystallization modulator in the blend, which contribute synergistically in the ternary blend to deliver a higher VOC, more efficient exciton generation, suppressed bimolecular charge recombination and enhanced charge transport, and an overall high photovoltaic performance. Very recently, non-fullerene acceptors (NFAs) based on low-bandgap small molecules have emerged as a new class of acceptors that rival the dominance of fullerene-based acceptors. Such discovery also stimulates promising device architectures such as ternary solar cells, with a handful that have achieved high power conversion efficiencies above 12%. The primary effort, however, has been focusing on low-bandgap NFAs that exploit complementary absorption and energy-level cascade. Herein we report a rare example of a wide-bandgap NFA that leads to high-performance ternary solar cells without relying on full absorption complementarity of all three components. Detailed studies revealed the multiple roles of this acceptor in blend films, which contribute synergistically to improved device characteristics. This work may inspire new design principles of potent wide-bandgap NFAs, which will open the door to high-efficiency organic photovoltaic devices through new opportunities such as multi-component solar cells. The marriage of non-fullerene acceptors (NFAs) and ternary solar cell architecture has brought about great advances in organic photovoltaics. The primary effort, however, has been focusing on low-bandgap NFAs that exploit complementary absorption and energy-level cascade. Here we report a wide-bandgap NFA IDT-T that functions as an energy-level mediator, a fluorescence resonance energy-transfer donor, an electron acceptor, and a crystallization modulator, which contribute synergistically in a ternary blend to yield high organic photovoltaic device performance.