The transition temperatures (Tt) and heats of crystallization (&Dgr;H) ofa‐Ge,a‐Si, anda‐Ge1−xSixfilms deposited by rf sputtering have been measured by differential scanning calorimetry (DSC). BothTtand &Dgr;H(per gram) increase linearly withxin the alloy system. Overlapping exothermic multiple peaks are observed in the DSC traces ofa‐Ge anda‐Si samples prepared at high deposition rates, suggesting that multiple amorphous configurations may coexist in these materials.