Advancing Integration of Direct C-H Arylation-Derived Star-Shaped Oligomers as Second Acceptors for Ternary Organic Solar Cells.

Organic solar cells (OSCs) could benefit from the ternary bulk heterojunction (BHJ), a method that allows for fine-tuning of light capture, cascade energy levels, and film shape, in order to increase their power conversion efficiency (PCE). In this work, the third components of PM6:Y6 and PM6:BTP-eC9 BHJs are a set of four star-shaped unfused ring electron acceptors (SSUFREAs), i.e., BD-IC, BFD-IC, BD-2FIC, and BFD-2FIC, that are facilely synthesized by direct C-H arylation. The four SSUFREAs all show complete complementary absorption with PM6, Y6, and BTP-eC9, which facilitates light harvesting and exciton collection. When BFD-2FIC is added as a third component, the PCEs of PM6:Y6 and PM6:BTP-eC9 binary BHJs are able to be improved from 15.31% to 16.85%, and from 16.23% to 17.23%, respectively, showing that BFD-2FIC is useful for most effective ternary OSCs in general, and increasing short circuit current (JSC) and better film morphology are two additional benefits. The ternary PM6:Y6:BFD-2FIC exhibits a 9.7% percentage of increase in PCE compared to the PM6:Y6 binary BHJ, which is one of the highest percentage increases among the reported ternary BHJs, showing the huge potential of BFD-2FIC for ternary BHJ OSCs.

Engineering electronic structures and optical properties of a MoSi2N4 monolayer via modulating surface hydrogen chemisorption.

Recently, a MoSi2N4 monolayer has been successfully synthesized by a delicately designed chemical vapor deposition (CVD) method. It exhibits promising (opto)electronic properties due to a relatively narrow bandgap (∼1.94 eV), high electron/hole mobility, and excellent thermal/chemical stability. Currently, much effort is being devoted to further improving its properties through engineering defects or constructing nanocomposites (e.g., van der Waals heterostructures). Herein, we report a theoretical investigation on hydrogenation as an alternative surface functionalization approach to effectively manipulate its electronic structures and optical properties. The calculation results suggested that chemisorption of H atoms on the top of N atoms on MoSi2N4 was energetically most favored. Upon H chemisorption, the band gap values gradually decreased from 1.89 eV (for intrinsic MoSi2N4) to 0 eV (for MoSi2N4-16H) and 0.25 eV (for MoSi2N4-32H), respectively. The results of optical properties studies revealed that a noticeable enhancement in light absorption intensity could be realized in the visible light range after the surface hydrogenation process. Specifically, full-hydrogenated MoSi2N4 (MoSi2N4-32H) manifested a higher absorption coefficient than that of semi-hydrogenated MoSi2N4 (MoSi2N4-16H) in the visible light range. This work can provide theoretical guidance for rational engineering of optical and optoelectronic properties of MoSi2N4 monolayer materials via surface hydrogenation towards emerging applications in electronics, optoelectronics, photocatalysis, etc.

Immobilization of Polymers to Surfaces by Click Reaction for Photocatalysis with Recyclability.

A surface-bound photocatalyst offers advantages of reusability and recyclability with ease. While it can be immobilized by spin coating or drop-casting, a more reliable and durable method involves the formation of a self-assembled monolayer (SAM) on a suitable surface using designer molecules. In this paper, we report devising a practical, durable, and recyclable photocatalytic surface using immobilized polytriazoles of diketopyrrolopyrrole (DPP). While the SAM formation techniques were utilized for superior results, conventional coatings of polymers on surfaces were performed for comparison. Different methods confirmed efficient immobilization and high grafting density for the SAM technique. Computational models suggested favorable energy parameters for active materials. Photocatalytic studies were performed using both immobilized polymers and polymers in solution for comparison. These findings are important for understanding various physicochemical characteristics of polytriazole-functionalized surfaces.

Experimental and Theoretical Investigations of Different Diketopyrrolopyrrole-Based Polymers.

Diketopyrrolopyrrole (DPP)-based polymers are often considered as the most promising donor moiety in traditional bulk heterojunction solar cell devices. In this paper, we report the synthesis, characterization of various DPP-based copolymers with different molecular weights, and polydispersity where other aromatic repeating units (phenyl or thiophene based) are connected by alternate double bonds or triple bonds. Some of the copolymers were used for device fabrication and the crucial parameters such as fill factor (FF) and open circuit voltage (V oc) were calculated. The density functional theory was used to optimize the geometries and deduce highest occupied molecular orbital-lowest unoccupied molecular orbital gaps of all the polymers and theoretically predict their optical and electronic properties. Optical properties of all the polymers, electrochemical properties, and band gaps were also obtained experimentally and compared with the theoretically predicted values.