Direct observation of the formation of silver precipitations by means of electron diffraction

Thin films (20-1,000 A) of copper (I)-, silver, and lead(II)-halides were prepared by evaporation onto silver (III), gold (III), and PbTe (III)-surfaces. These films were irradiated in vacuo with 40 kV-electrons, in some cases also with the light of a Xenon-lamp. At the same time the diffraction pattern, produced by the electron beam at glancing incidence, was observed and registered photographically. Silver precipitates could be detected by their diffraction pattern, when the crystallites had grown to a size of about 50 A. From all materials investigated silveriodide showed maximum sensitivity. The precipitates formed show no orientation with respect to the host crystal. From the temperature dependence of the sensitivity an activation energy of 0.12 eV can be deduced leading to interstitial ion migration as rate determining step. Pure silverchloride can not been radiolyzed by 40 kV-electrons. After doping it with 0.3 mol% CaCl2 or MgCl2 it becomes very sensitive. The precipitate showes orientation with respect to the host lattice. Also pure CuJ is resistant against the electron beam. Mixed crystals (Ag, Cu)J with xsub(AgJ) > 0.5 behave similar as pure AgJ. Pb(II)-halides show no sensitivity, but the compounds AgBr x 2 PbBr2 and 5 AgJ x PbJ2 are readily radiolyzed, forming polycrystalline silver precipitates. The mechanism of radiolysis, its dependency on temperature and film thickness is discussed. (orig.)