EPR Study of Hole-Trapping at Cation Vacancies in Silver-Halides

The hole-trapping at cation vacancies in silver halides is studied by means of electron paramagnetic resonance (EPR). The studied silver halide crystals were doped with trivalent Fe, and also with one of the divalent ions Ca, Cd, or Zn. The former dopant is to serve as a hole source upon sub-band-gap irradiation, while the latter increases the concentration of silver vacancies in the crystal. In AgCl, the photo-hole is observed to become self-trapped at a silver ion at a regular lattice site near a cation vacancy. The thermal stability of the resulting vacancy-perturbed self-trapped hole (STH) is found to be substantially enhanced by the presence of the nearby vacancy. Due to the close similarity of the EPR spectrum of the new centers to that of the normal STH, the existence of the vacancy-perturbed STH centers is further confirmed by isochronal annealing experiments. By comparing the intensities of the 20K STH spectra after annealing at successively higher temperatures, it is demonstrated that, in fact, there exist two types of vacancy-perturbed STH centers, one of which decays at 70K and the other survives up to a higher temperature (110K). In addition, by computer simulation, the position of the perturbing vacancy is determined to be located at the next-nearest-neighbor position for the less stable perturbed STH. On the other hand, in AgBr, no corresponding effects have been seen here. This result is in contrast to what is expected from Kanzaki's optical absorption experiments, in which an absorption line was assigned to a hole trapped near a cation vacancy in AgBr. The metastable nature of the self-trapped hole state in AgBr might probably provide explanation for the absence of such a resonance, even with the stabilizing effect of a nearby silver vacancy.