Regioisomer-Free Difluoro-Monochloro Terminal-based Hexa-Halogenated Acceptor with Optimized Crystal Packing for Efficient Binary Organic Solar Cells.

Herein, we synthesized new hetero-halogenated end groups with well-determined fluorinated and chlorinated substitutions (o-FCl-IC and FClF-IC), and synthesized regioisomer-free small molecular acceptors (SMAs) Y-Cl, Y-FCl, and Y-FClF with distinct hetero-halogenated terminals, respectively. The single-crystal structures and theoretical calculations indicate that Y-FClF exhibits more compact three-dimensional network packing and more significant π-π electronic coupling compared to Y-FCl. From Y-Cl to Y-FCl to Y-FClF, the neat films exhibit a narrower optical band gap and gradually enhanced electron mobility and crystallinity. The PM6 : Y-FClF blend film exhibits the strongest crystallinity with preferential face-on molecular packing, desirable fibrous morphology with suitable phase segregation, and the highest and balanced charge mobilities among three blend films. Overall, the PM6 : Y-FClF organic solar cells (OSCs) deliver a remarkable efficiency of 17.65 %, outperforming the PM6 : Y-FCl and PM6 : Y-Cl, which is the best PCE for reported hetero-halogens-based SMAs in binary OSCs. Our results demonstrate that difluoro-monochloro hetero-terminal is a superior regio-regular unit for enhancing the intermolecular crystal packing and photovoltaic performance of hetero-halogenated SMAs.

A Synergistic Strategy of Manipulating the Number of Selenophene Units and Dissymmetric Central Core of Small Molecular Acceptors Enables Polymer Solar Cells with 17.5 % Efficiency.

A dissymmetric backbone and selenophene substitution on the central core was used for the synthesis of symmetric or dissymmetric A-DA'D-A type non-fullerene small molecular acceptors (NF-SMAs) with different numbers of selenophene. From S-YSS-Cl to A-WSSe-Cl and to S-WSeSe-Cl, a gradually red-shifted absorption and a gradually larger electron mobility and crystallinity in neat thin film was observed. A-WSSe-Cl and S-WSeSe-Cl exhibit stronger and tighter intermolecular π-π stacking interactions, extra S⋅⋅⋅N non-covalent intermolecular interactions from central benzothiadiazole, better ordered 3D interpenetrating charge-transfer networks in comparison with thiophene-based S-YSS-Cl. The dissymmetric A-WSSe-Cl-based device has a PCE of 17.51 %, which is the highest value for selenophene-based NF-SMAs in binary polymer solar cells. The combination of dissymmetric core and precise replacement of selenophene on the central core is effective to improve Jsc and FF without sacrificing Voc .

Modulating Crystal Packing, Film Morphology, and Photovoltaic Performance of Selenophene-Containing Acceptors through a Combination of Skeleton Isomeric and Regioisomeric Strategies.

Here, we report a series of acceptor-donor-acceptor (A-D-A) architecture isomeric acceptors (SeCT-IC, CSeT-IC, and CTSe-IC), which have an identical electron-deficient terminal A-group and three different central D-cores with the selenophene at the innermost, relatively outer, and outermost positions of the central core, respectively. From CSeT-IC to the atom regioisomer of CTSe-IC and to the conjugated skeleton isomer of SeCT-IC, the optical band gap of neat films continuously reduced and highest occupied molecular orbitals (HOMO) gradually upshifted with changing the selenophene from relatively outer position to the outermost position and to the innermost position of the central core. More importantly, the single-crystal structure and the GIWAXS measurements revealed that CTSe-IC presents the closest π-π stacking distance, the largest CCL, and the best molecular order and crystallinity, which led to the highest electron mobility in neat films. Furthermore, the J71:CTSe-IC blend film presents a more ordered film morphology with more proper phase separation domain size, more dominant face-on orientation, and relatively higher and more balanced electron-hole mobilities in comparison with that of J71:SeCT-IC and J71:CSeT-IC. Consequently, the J71:CTSe-IC-based organic solar cell gave a superior power conversion efficiency (PCE) of 11.59%, which was obviously higher than those for J71:SeCT-IC (10.89%) and J71:CSeT-IC (8.52%). Our results demonstrate that the acceptor with selenophene in the outermost position led to significantly enhance the PCE. More importantly, rational modulation of the central fused core in combination with the conjugated skeleton isomeric method and the atom regioisomeric method provides an effective way to understand the structure-crystallinity-photovoltaic property relationship of selenophene-based regioisomers.

Two-Dimensional Conjugated Benzo[1,2-b:4,5-b']diselenophene-Based Copolymer Donor Enables Large Open-Circuit Voltage and High Efficiency in Selenophene-based Organic Solar Cells.

A two-dimensional electron-rich fused-ring moiety (ClBDSe) based on benzo[1,2-b:4,5-b']diselenophene is synthesized. Three copolymers (PBDT-Se, PBDSe-T, and PBDSe-Se) are obtained by manipulating the connection types and number of selenophene units on the conjugated main chains with two 2D fused-ring units and two different π-bridges, respectively. In comparison with PBDT-Se and PBDSe-Se, PBDSe-T with benzo[1,2-b:4,5-b']diselenophene unit and thiophene π-bridge exhibits the deepest HOMO energy level and the strongest crystallinity in neat films. The PBDSe-T:Y6 blend film exhibits the best absorption complementarity, the most distinctive face-on orientation with proper phase separation, the highest carrier mobilities, and the lowest charge recombination among three blend films. Finally, the PBDSe-T:Y6-based device delivers an impressive power conversion efficiency (PCE) of 14.50 %, which is higher than those of PBDT-Se:Y6 and PBDSe-Se:Y6. Moreover, a decent open-circuit voltage (Voc ) of 0.89 V with a remarkably small energy loss of 0.44 eV is achieved for PBDSe-T:Y6. The efficiency of 14.50 % is the highest value for selenophene-containing copolymer-based binary organic solar cells (OSCs). This study provides evidence that introduction of 2D-benzo[1,2-b:4,5-b']diselenophene as a fused electron-rich unit with π-bridging into copolymeric donors is a valid strategy for providing high Voc and excellent PCE simultaneously in selenophene-based OSCs.