Molecular Engineering Strategies of Spectral Matching and Structure Optimization for Efficient Metal-Free Organic Dyes in Dye-Sensitized Solar Cells: A Theoretical Study.

Metal-free organic dyes are promising dyes that can be applied widely in dye-sensitized solar cells (DSSCs). The rational design and selection of dyes with complementary absorption can promote the development of methods that can enhance the utilization of incident light by DSSCs, such as cosensitization and tandem devices. Based on these opinions, the structure of the reported high-performance metal-free organic dye ZL003 is used as a template to design two new metal-free organic dyes, HX-1 and HX-2, by replacing its donor unit with a 2-phenothiazine-phenylamine unit and fusing its three independent π-bridge units into a whole with the aim of driving the red shift and the blue shift of the absorption spectra of ZL003, respectively. Through theoretical investigation, it is demonstrated that the perfect complementary optical absorption of HX-1 and HX-2 can be realized as the shift of the absorption spectra of ZL003 to different directions, which means their feasibility to the application in cosensitization or tandem dye-sensitized solar cells (T-DSSCs). Furthermore, it is hypothesized that HX-1 may be the dye with better photovoltaic performance than ZL003 by modeling their intramolecular charge-transfer (ICT) processes, TiO2 surface adsorption, and photovoltaic parameters. The short-circuit current density (Jsc) and photoelectric conversion efficiency (PCE) of HX-1 are 23.10 mA·cm-2 and 21.26% in theory, compared to those of 20.68 mA·cm-2 and 19.64% in ZL003 at the same computational level, respectively. In view of the complementary optical properties, the combination of HX-1 with HX-2 may be a reasonable option for dyes for the development of a highly efficient cosensitization system or T-DSSCs in the future. In terms of such findings, these two novel metal-free organic dyes may have bright prospects in the research of highly efficient DSSCs, and this work can provide a reference for the design of dyes with complementary absorption through simple structural adjustments of the realistic dyes with high photovoltaic performance.

Unusual solute segregation phenomenon in coherent twin boundaries.

Interface segregation of solute atoms has a profound effect on properties of engineering alloys. The occurrence of solute segregation in coherent twin boundaries (CTBs) in Mg alloys is commonly considered to be induced by atomic size effect where solute atoms larger than Mg take extension sites and those smaller ones take compression sites in CTBs. Here we report an unusual solute segregation phenomenon in a group of Mg alloys-solute atoms larger than Mg unexpectedly segregate to compression sites of {10[Formula: see text]1} fully coherent twin boundary and do not segregate to the extension or compression site of {10[Formula: see text]2} fully coherent twin boundary. We propose that such segregation is dominated by chemical bonding (coordination and solute electronic configuration) rather than elastic strain minimization. We further demonstrate that the chemical bonding factor can also predict the solute segregation phenomena reported previously. Our findings advance the atomic-level understanding of the role of electronic structure in solute segregation in fully coherent twin boundaries, and more broadly grain boundaries, in Mg alloys. They are likely to provide insights into interface boundaries in other metals and alloys of different structures.