The mechanism of nucleation and growth from CdGeAs2 glass

Distinctively different microstructures were obtained depending on the heating rate to which CdGeAs₂ glasses were exposed during the devitrification process. Differential scanning calorimetry showed that under very slow heating rates, the single crystallization peak splits into three superimposed exotherms. Quenching from the temperature at which selected features appear on the DSC trace and using X-ray diffraction and transmission electron microscopy interactively, demonstrated the initial formation of a metastable doped precursor germanium crystalline phase. This crystalline structure continued to grow until it could no longer accommodate the impurities, and the transformation terminated. These regions then acted as heterogeneous nucleation sites for the growth of chalcopyrite structured CdGeAs₂ with a spherulitic microstructure. The spherulites grew as stacked plates from the nucleation site. At higher temperatures, the metastable germanium structure converted, growing backwards toward the center of each precursor, into the stable chalcopyrite structure, permitted by appropriate ionic diffusion shifting composition toward stoichiometry. At faster heating rates, less of these germanium precursors formed, creating a visually bimodal grain size distribution in the microstructure, as compared to slower heating rates. Using the simplex algorithm, the mechanism and activation energy of each reaction are reported as well as the deconvoluted enthalpies of each transformation.