The development of efficient redox-photosensitizers based on the earth-abundant metal ions as an alternative toward noble- and/or rare-metal based photosensitizers is very desirable. In recent years, heteroleptic diimine-diphosphine Cu(I) complexes have been well investigated as one of the most remarkable candidates because of their great potentials as efficient photosensitizers. Here, we investigated the effects of the structure of the diphosphine ligands on the photosensitizing abilities using a series of Cu(I) complexes bearing 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (dmpp) and various diphosphine ligands in order to explore the suitable structure for the photosensitizing reactions. The number of methylene chains between the two phosphorous atoms in the diphosphine ligands was systematically changed from two to four, and the relationship between the length of the carbon chains and the photosensitizing abilities were investigated by conducting photocatalytic CO 2 reduction with the Cu(I) complexes as photosensitizers. Turnover frequencies of the CO 2 reduction drastically increased with increasing the length of the carbon chains. The systematic study herein reported suggests that the large P-Cu-P angles should be one of the most important factors for enhancing the photosensitizing abilities.

The reflow phenomenon of Cu interconnections deposited over via holes was analyzed by viscoelastic deformation simulation using a finite-element method to clarify the embedding mechanism of Cu interconnections into via holes in a novel dual-damascene fabrication technology, which combined sputter deposition and high-pressure annealing. Cu is considered to be a viscoelastic body, and the stress distribution and deformation behavior of Cu interconnections were calculated. As a result, the deformation behavior of the Cu interconnections exhibited close agreement between the calculated and the observed values. From our series of results, we inferred that Cu interconnections are embedded into via holes by the creep deformation mechanism defined in this study during the high-pressure annealing process.

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