An EPR study of two-electron sensitization by fragmentable electron donors

Fragmentable electron donors (FEDs) are molecules designed to undergo bond fragmentation after capturing the hole created by photoexposure of silver halide. By design, the radical remaining after fragmentation is a potent reductant expected to be capable of injecting an electron into the conduction band of the silver halide. Thus, the addition of a FED to the AgX surface should allow the creation of two electrons for each photon absorbed by the substrate. Photographic studies have confirmed that the addition of FEDs can increase the photosensitivity of AgX materials. In this work, EPR spectroscopy was employed to study the processes of hole capture, donor fragmentation, and secondary electron injection by FEDs in AgBr dispersions. To do so, we used AgBr microcrystals doped with diamagnetic transition metal complexes that act as deep electron traps. For samples exposed to actinic light at 15 K, secondary electron injection was detected as an increase in the EPR signal from electrons trapped at the dopant upon annealing the samples above 50 K. Organic radical intermediates and self-trapped hole centers were the other paramagnetic species monitored in this study. The results presented here confirm that the FED sensitization mechanisms originally proposed by Gould et al. take place at silver halide surfaces and result in additional electrons in the silver halide conduction band.