Effect of vacuum annealing and substrate temperature on structural and optical properties of ZnIn2Se4 thin films

Zinc indium selenide (ZnIn2Se4) thin films were prepared by the thermal evaporation technique with high deposition rate. The effect of thermal annealing in vacuum on the crystallinity of the as-deposited films was studied at different temperatures (523, 573 and 623 K). The effect of substrate temperature (623 K) for different thickness values (173, 250, 335 and 346 nm) on the optical parameters of ZnIn2Se4 was also studied. The structural studies showed nanocrystalline nature of the room temperature (300 K) deposited films with crystallite size of about a few nanometers. The crystallite size increased up to 31 nm with increasing the annealing temperature in vacuum. From the reflection and transmission data, the refractive index n and the extinction coefficient k were estimated for ZnIn2Se4 thin films and they were found to be independent of film thickness. Analysis of the absorption coefficient data of the as-deposited films revealed the existence of allowed direct and indirect transitions with optical energy gaps of 2.21 eV and 1.71 eV, respectively. These values decreased with increasing annealing temperature. At substrate temperature of 623 K, the direct band gap increased to 2.41 eV whereas the value of indirect band gap remained nearly unchanged. The dispersion analysis showed that the values of the oscillator energy Eo, dispersion energy Ed, dielectric constant at infinite frequency ε∞, and lattice dielectric constant εL were changed appreciably under the effect of annealing and substrate temperature. The covalent nature of structure was studied as a function of the annealing and substrate temperature using an empirical relation for the dispersion energy Ed. Generalized Miller's rule and linear refractive index were used to estimate the nonlinear susceptibility and nonlinear refractive index of the thin films.