Microstructural evolution of ZnS during sintering monitored by optical and positron annihilation techniques

Positron lifetime and optical absorption techniques were employed to track the microstructural evolution of polycrystalline ZnS grown by Chemical Vapor Deposition (CVD). As grown material and material treated with Hot Isostatic Pressure (HIP) was sintered at temperatures ranging from 400 to 1000°C for 2–18 h. A 290 ps defect lifetime could be resolved in all samples, while an additional longer lifetime (τ=430 ps) was found only in samples annealed at low temperatures. This component gradually disappeared during annealing at 800°C. Associated with the disappearance of the long-lived component, the apparent bulk lifetime of the material changed from 235 to 215 ps. A 215±2 ps bulk parameter was also found for HIP-treated material annealed at temperatures greater than 400°C and hence is taken to represent the delocalized state of the positrons in ZnS. Optical absorption measurements showed that annealing at 800°C also caused the absorption profiles of the CVD and HIP samples to converge. The rate of the bulk lifetime transition correlates with the absorption changes. The observed sharpening of the absorption profile is attributed to a decrease in scattering from grain boundaries and voids, and a decrease in absorption from point defects. The 430 ps lifetime is believed to be due to trapping at voids and grain boundaries, while the 290 ps lifetime likely is due to a monovacancy stabilized as a small complex.