Chalcogenide glasses have received lots of attention because of their superior optical properties. To optimize these properties and expand areas of applications, more studies are required to establish the extent to which the parameters can be tuned over a wide range of annealing temperatures and heating rates. To do this, bulk and thin ∼150 nm As30Te67Ga3 films were prepared by melt-quenching and thermal evaporation techniques,respectively. The phase transition was investigated using differential scanning calorimeter (DSC) while the crystal structures were studied by X-ray diffraction (XRD). Characteristic temperatures such as the glass transition, crystallization and melting temperature of the bulk glass were found to depend on the heating rate. The activation energy of glass transition was 167.29 kJ/mol while the energy of crystallization was 103.98 kJ/mol. XRD results indicated that the annealed films showed more crystallinity, larger average crystallite size, lower dislocation density and lower strain as annealing temperature increased. According to the Avrami exponent, a combination of two and three-dimensional crystal growth with heterogeneous nucleation are possible mechanisms for the crystallization process. Moreover, optical constants such as the optical band gap, refractive index, extinction coefficient, high-frequency dielectric constants, real and imaginary parts of dielectric constants were found to strongly depend on the annealing temperature. The optical energy gap decreased from 1.1 to 0.89 eV as the annealing temperature increased from 373 to 433K. These results indicate that thermal annealing is a major factor that can be used to tune the crystal structure, and hence the optical properties of
As30Te67Ga3 system.