Sputtered amorphous Ag0.055 In0.065 Sb0.59 Te0.29, Ge4 Sb1 Te5, and Ge2 Sb2 Te5 thin films were studied by differential scanning calorimetry. The crystallization temperature and the heat of crystallization of the amorphous phases, the melting temperature and the heat of fusion of the crystalline phases, and the heat capacities of crystalline and liquid AgInSbTe were measured. The entropies of fusion are large (≥2R), which suggests a change of bonding type between liquid and crystal. In contrast to amorphous AgInSbTe and Ge4 Sb1 Te5, which upon heating crystallize to a single phase within a small temperature interval, the crystallization of amorphous Ge2 Sb2 Te5 is complicated by a subsequent cubic-to-hexagonal transformation. No thermal evidence of a glass transition was found below the crystallization temperature. The ratio of the glass transition temperature (approximated as the crystallization temperature) to the liquidus temperature is 0.49–0.56, which identifies the materials as marginal glass formers. The heat capacity measurements on AgInSbTe were used to estimate the temperature dependence of the difference in enthalpy, entropy, and Gibbs free energy between the undercooled liquid and the crystal. © 2003 America- n Institute of Physics.